Polymeric substrate containing mercapto and sulfonic groups

ABSTRACT

A catalyst useful for the condensation of an aldehyde or ketone starting material with a phenol is an insoluble mercaptosulfonic acid compound. The heterogeneous catalysts comprise catalytically-active species represented by the formula: ##STR1## L is an optional linking group and -- is a bond, which catalytically-active species is attached by the bond -- to an insoluble organic or inorganic support; 
     or a catalytically-active species represented by the formula: ##STR2## wherein L&#39; is an optional linking group, -- is a bond and θ&#39; and θ&#34; are residues of θ, and a and b are independently selected from integers equal to or greater than 1.

This application is a continuation of Ser. No. 08/468,863 filed Jun. 6,1995, now abandoned, which is a continuation of Ser. No. 08/298,622filed Aug. 31, 1994, now U.S. Pat. No. 5,463,140.

BACKGROUND OF THE INVENTION

This invention relates to preparation of polyphenols, more particularlyto the preparation of polyphenols from ketones or aldehydes and phenols.

Acid-catalyzed condensation of phenols with aldehydes or ketones is wellknown. Acid catalysts include acidic ion exchange resin catalysts andsoluble acid catalysts. Soluble acid catalysts can be, for example,hydrogen chloride, sulfuric acid, hydrochloric acid, phosphoric acid,hydrobromic acid, nitric acid, dimethyl sulfate, sulfur dioxide,4-toluenesulfonic acid, boron trifluoride, alkanesulfonic acids, borontrifluoride complexes and other acid-acting compounds, includingcompounds which are hydrolyzed by water to form acids, e.g. aluminumchloride, sulfonyl chloride and phosgene.

A number of compounds are known to promote such an acid-catalyzedcondensation. These promoters include mercaptan groups which are eitherfree or bound to a resin. Alkyl mercaptans and bis-mercaptoethanolamineare examples of reported promoters.

It has been proposed by Scriabine et al. (U.S. Pat. No. 2,923,744) toproduce Bisphenol A using sulfuric acid, promoted bymercaptoalkanesulfonic acids or salts or corresponding sulfonate estersat a level of 0.1-5% by weight of the base charge, to catalyzecondensation of acetone and phenols, when used in amounts of 0.1 to 5percent by weight based on total charge. Sulfuric acid is used inamounts of about 2 moles per mole of acetone.

Riemann et al. (U.S. Pat. No. 4,675,458) have proposed making9,9-bis-(4-hydroxyphenyl)fluorene in the presence of sulfuric acid,preferably concentrated sulfuric acid, and a mercaptan, particularly3-mercaptopropionic acid, as promoter.

Massirio et al. (U.S. Pat. No. 5,248,838) have disclosed the use of acombination of methanesulfonic acid and a mercaptan/mercaptoalkanoicacid for catalyzing the condensation of phenols with fluorenone. Highlevels of methanesulfonic acid with respect to the feed and themercaptan/mercaptoalkanoic acid, are used. The reactions can be run inhalogenated hydrocarbon solvents.

Bottenbruch et al. (U.S. Pat. No. 4,996,373) have proposed a process forproducing dihydroxyaryl compounds from carbonyl compounds and phenolsunder high pressure, in the presence of various catalysts, includingsulfonic acid resins. Catalysts containing sulfhydryl functionality,e.g. ion exchangers treated with mercapto compounds, have been disclosedfor this use.

Meyer et al. (U.S. Pat. No. 4,387,251) have proposed processes formaking 4,4'-dihydroxydiphenyl alkanes using aromatic sulfonic acids ascondensing agents. Mercapto groups are included within the definition ofR₃ and are characterized as being inert. Freitag et al. (U.S. Pat. No.5,210,328) disclose using the same types of sulfonic acid catalysts formaking cycloalkylidene bisphenols.

Jansen (U.S. Pat. No. 2,468,982) has proposed preparation of bisphenolsusing anhydrous hydrogen chloride in combination with a mercaptoalkanoicacid, which may be formed in situ by reaction of a mercaptol with theketone, as condensing agent.

Knebel et al. (U.S. Pat. No. 4,931,594) disclose the use of largeamounts of sulfonic acid resin, mixed with uncombined3-mercaptopropionic acid, to cause the condensation to occur.

It has been proposed in British Patent 1,185,223 to use a mixture ofinsoluble resins, one a sulfonic acid resin and the other a resincontaining mercapto groups, for making bisphenols.

Randolph et al. (U.S. Pat. No. 5,212,206) disclose a catalyst, made bytreating a sulfonated ion-exchange resin with a dialkylaminomercaptan.Other references, representative of references on modification ofsulfonic acid ion-exchange resins, include Wagner (U.S. Pat. No.3,172,916). McNutt et al. (U.S. Pat. No. 3,394,089), Faler et al. (U.S.Pat. Nos. 4,455,409; 4,294,995 and 4,396,728); Heydenrich et al. (U.S.Pat. No. 4,369,293); Berg et al. (U.S. Pat. No. 5,302,774) and Maki etal. (U.S. Pat. No. 4,423,252). The reactive catalysts generally includemercapto-functions attached to a sulfonic acid group in the form of asulfonamido or ammonium sulfonate salt.

Shaw (U.S. Pat. No. 4,859,803) discloses preparing bis-phenols fromphenol and a ketone in the presence of an acidic (sulfonic acid)ion-exchange resin and a mercaptan, the mercaptan being added atparticular locations of a specified reactor configuration to prevent theformation of cyclic dimers.

Li has disclosed (U.S. Pat. No. 4,825,010) isomerization of by-productsof condensates of phenols and ketones, using a catalytic amount ofacidic sulfonated cationic-exchange resin having sulfonic acid sitesionically bonded to alkylmercaptoamines. Other patents by Li (U.S. Pat.Nos. 4,822,923 and 5,001,281) further suggest the state of the art ofusing ion-exchange resins to isomerize by-products of bisphenolsyntheses.

Powell et al. (U.S. Pat. No. 5,105,026) disclose using acidicion-exchange resins to isomerize undesirable products of bisphenolsynthesis to desirable products, e.g. to Bisphenol A. Morgan (U.S. Pat.No. 3,546,165) has disclosed condensation of phenol with variousketones, including fluorenone and indanone, using high levels ofhydrochloric acid or hydrogen chloride, in the presence of minor amountsof 3-mercapto-propionic acid. The products are used for the preparationof polyester resins.

Szabolcs (U.S. Pat. Nos. 4,467,122 and 4,503,266) discloses washingcrude product, containing BHPF, from a hydrochloric acid/zinc chloridecatalyzed process, to B remove HCl, ZnCl₂ and excess phenol, prior torecrystallization from dichloroethane. See also the abstract for DE OLS2,948,222 (7/30/81).

Korshak et al. (SU 172,775) disclose washing a mixture of phenol, BHPFand HCl with water, after which phenol is removed by distillation.

The following references, herein incorporated by reference, disclose thepreparation of resins, containing sulfonic acid functionality,introduced either by copolymerization or by sulfonation afterpolymerization:

    ______________________________________                                        U.S. Pat. No. 3,205,285                                                                            Turbak et al.                                              U.S. Pat. No. 3,366,711 Mazzolini et al.                                      U.S. Pat. No. 3,426,104 Masson                                                U.S. Pat. No. 4,587,304 Thaler et al.                                         U.S. Pat. No. 4,764,557 Eichenauer et al.                                   ______________________________________                                    

Trapasso (U.S. Pat. No. 3,706,707) discloses the preparation of adductsfrom a polymerized cyclic ether and a sultone. Dean (U.S. Pat. No.4,568,724) is of similar interest with respect to reaction products froman EPDM rubber and a sultone.

Welch (U.S. Pat. No. 3,029,221) and Niwa et al. (U.S. Pat. No.4,912,170) disclose processes for modifying polystyrene resins.

It is an object of this invention to provide a process for thecondensation of aldehydes or ketones with phenols, to achieve highyields of preferred bis-(4-hydroxyaryl) isomers with low reaction timeswhile avoiding use of strong inorganic acids.

Further objects of the invention include the development of processesfor the synthesis of polyphenols, characterized by high yields of highpurity products under reaction conditions, which are not corrosive tovessels in which the processes are conducted. In addition, avoiding theuse of sulfuric acid, eliminates the possibility of side reactions,including sulfonation of phenols.

DISCLOSURE OF THE INVENTION

In one aspect, this invention relates to a process for the condensationof an aldehyde or ketone starting material with a phenol, unsubstitutedin at least one position, comprising reacting the aldehyde or ketonestarting material with the phenol in a reaction mixture in the presenceof a soluble or insoluble mercaptosulfonic acid compound underconditions sufficient to bring about formation of a geminal bisphenolicmoiety at each aldehyde or ketone moiety in the starting material;

provided that the soluble mercaptosulfonic acid compound ischaracterized by the formula

    (HS).sub.a --θ--(SO.sub.3 H).sub.b

wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene,alkylenecycloaliphatic, alkylenearyl, heterocyclic oralkyleneheterocyclic residue and a and b are independently selected fromintegers from 1 to about 20; and

the insoluble mercaptosulfonic acid comprises a catalytically-activespecies represented by the formula ##STR3## in which θ' is an alkylene,cycloaliphatic, arylene, alkylenearylene, alkylenecycloaliphatic,alkylenearyl, heterocyclic or alkyleneheterocyclic residue; a and b areindependently selected from integers from 1 to about 20; L is anoptional linking group and--is a bond, which catalytically-activespecies is attached by the bond--to an insoluble organic or inorganicsupport;

or a catalytically-active species represented by the unit formula##STR4## wherein θ" is an alkylene, arylene, cycloaliphatic,alkylenearylene, alkylenecycloaliphatic, alkylenearyl, heterocyclic oralkyleneheterocyclic residue; a and b are independently selected fromintegers from 1 to about 20; L' is an optional linking group and--is abond.

This invention further relates to novel catalytically-active polystyreneresins, characterized by bearing at least one of each of a mercaptofunction and a sulfonic acid function on some individual styrene unitsof a polymer chain.

In yet another aspect, this invention relates to processes for preparingthe catalytically-active polystyrene resins. These processes preferablycomprise steps of (b) sulfonating a haloalkylpolystyrene to produce anintermediate having sulfo functional groups; (c) optionally convertingthe sulfo functional groups to corresponding alkali metal salts; (d)thiolating the thus-produced sulfostyrene intermediate by reacting thehalo function with a reactive thiolate to produce a correspondingmercapto group or precursor thereof;(e) optionally hydrolyzing thethus-thiolated intermediate with an acid or base when the thiolatedgroup so requires and (f) optionally acidifying (if so required) toproduce sulfonic acid functional groups units.

The process of the invention permits use of very low levels of a singleacidic condensing agent. The process permits simplified productisolation procedures, recycle procedures, and/or waste management. Theprocess does not require a neutralization step to remove hydrochloric orsulfuric acid and does not produce a waste salt stream. The acidiccondensing agents used in the process of this invention are readilyremoved from the reaction mixtures and can be recovered and recycled.

The process of this invention results in high selectivity towardpreferred bis-(4-hydroxyaryl) isomers and very fast reaction rates.

The process of this invention is particularly useful for the preparationof bis(hydroxyaryl) compounds, such as bisphenol A and9,9-bis-(4-hydroxyphenyl)fluorene, both of which are useful in thepreparation of polycarbonates and other commercially significantpolymers.

The heterogeneous catalysts disclosed herein advantageously are morereactive than heterogeneous catalysts currently used. Theyadvantageously allow using lower temperatures with correspondinglygreater selectivity for desired product than is currently experienced.Greater selectivity reduces purification necessary to produce a desiredor preselected purity of product. Thus for a commercially producedbisphenol like Bisphenol A, a heterogeneous catalyst disclosed hereincan be advantageously substituted in an existing commercial process, runwith the same or higher throughput at a lower temperature with lesspurification to achieve at least equally pure product.

DETAILED DESCRIPTION OF THE INVENTION

Ketones or aldehydes and phenolic compounds (hereinafter phenol,phenols, a phenol or phenolic starting material) useful in process ofthe invention are known in the art and are described in the literature,for instance Jansen '982, supra, Maki et al., '252, supra, Morgan '165,supra, and Knebel et al. '594, supra, all of which are hereinincorporated by reference.

The condensations of this invention can be represented by the equationfor a representative condensation, that of phenol with 9-fluorenone:##STR5##

The process for making bisphenol A can be represented by the equation:##STR6##

Phenol starting materials are advantageously any aromatic hydroxycompounds which have at least one unsubstituted position, and optionallyhave one or more inert substituents such as hydrocarbyl or halogen atthe one or more ring positions. An inert substituent is a substituentwhich does not interfere undesirably with the condensation of the phenoland ketone or aldehyde and which is not, itself, catalytic. Preferably,the phenols are unsubstituted in the position, para to the hydroxylgroup.

Alkylene (alk), alkyl, cycloaliphatic, aryl, arylene (ar), alkylarylene(alkar), arylalkylene (aralk), alkylcycloaliphatic andalkylenecycloaliphatic are hydrocarbyl functions, that is, functionscontaining carbon and hydrogen atoms. The alkylene functions can bestraight or branched chain and saturated or unsaturated, that isalkylene, alkenylene, or alkynylene. Cycloaliphatic hydrocarbon residuesinclude both saturated and unsaturated cyclic residues, that is,cycloalkylene and cycloalkenylene. Arylene includes mono- and polycyclicaromatic residues, e.g. those of benzene, biphenyl, biaryl, naphthyl,phenanthrenyl, anthracenyl or aryl groups, including those bridged by analkylene group. Alkaryl residues include alkyl, alkenyl andalkynyl-substituted aromatic rings. Aralkyl includes alkyl, alkenyl oralkynyl residues, substituted by one or more aromatic groups.

Alkyl groups include both straight- and branched-chain isomers ofmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, nonadecyl and eicosyl groups, as well as the correspondingunsaturated (alkenyl or alkynyl) groups, as well as higher homologues.Preferably, the alkyl groups are of 1-20 carbon atoms, more preferablyof 1-5 carbon atoms, most preferably those of 1-3 carbon atoms. Alkyl of1-5 carbon atoms includes the various methyl, ethyl, propyl, butyl andpentyl isomers.

Alkyl, aryl, alkaryl and aralkyl substituents are suitable hydrocarbylsubstituents on the phenol reactant.

Other inert substituents on the phenols include, but are not limited toalkoxy, aryloxy or alkaryloxy, wherein alkoxy includes methoxy, ethoxy,propyloxy, butoxy, pentoxy, hexoxy, heptoxy, octyloxy, nonyloxy,decyloxy and polyoxyethylene, as well as higher homologues; aryloxy,phenoxy, biphenoxy, naphthyloxy, etc. and alkaryloxy includes alkyl,alkenyl and alkylnyl-substituted phenolics.

Additional inert substituents on phenols include halo, such as bromo,chloro or iodo.

Cyano and nitro substituents may deactivate the phenols and aldehyde andcarboxylic acid substituents may cause interfering reactions. Additionalhydroxyl substituents may be suitable in some cases.

Preferred substituents include alkyl moieties containing from 1 to about10 carbon atoms, more preferably, lower alkyl moieties, containing from1 to about 5 carbon atoms, most preferably from 1 to 3 carbon atoms. Thealkyl substituents may be straight or branched chain isomers.

Exemplary phenols include, but are not limited to, phenol, 2-cresol,3-cresol, 4-cresol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol,2-tert-butylphenol, 2,4-dimethylphenol, 2-ethyl-6-methylphenol,2-bromophenol, 2-fluorophenol, 2-phenoxyphenol, 3-methoxyphenol,2,3,6-trimethylphenol, 2,3,5,6-tetramethylphenol, 2,6-xylenol, 2,6-dichlorophenol, 3,5-diethylphenol, 2-benzylphenol,2,6-di-tertbutylphenol, 2-phenylphenol, 1-naphthol, 2-naphthol and thelike. Preferred phenols include phenol, 2- or 3-cresol,2,6-dimethylphenol, resorcinol, naphthols, and mixtures thereof. Mostpreferably, the phenol is unsubstituted.

The ketones which are advantageously used include any ketone having asingle ketone carbonyl (C═O) group or several ketone carbonyl groups,and which are reactive under the conditions used. The ketones can besubstituted with substituents, which are inert under the conditionsused. Inert substituents are as set forth above for the reactivephenols.

The ketones are advantageously selected from aliphatic, aromatic,alicyclic or mixed aromatic-aliphatic ketones, diketones or polyketones,of which acetone, methyl ethyl ketone, diethyl ketone, benzil,acetylacetone, methyl isopropyl ketone, methyl isobutyl ketone,acetophenone, ethyl phenyl ketone, cyclohexanone, cyclopentanone,benzophenone, fluorenone, indanone, 3,3,5-trimethylcyclohexanone,anthraquinone, 4-hydroxyacetophenone, acenaphthenequinone, quinone,benzoylacetone and diacetyl are representative examples.

Ketones having halo, nitrile or nitro substituents can also be used, forexample, 1,3-dichloroacetone or hexafluoroacetone.

Aliphatic ketones which are useful starting materials include, but arenot limited to acetone, ethyl methyl ketone, isobutyl methyl ketone,1,3-dichloroacetone, hexafluoroacetone and the like. A preferredaliphatic ketone is acetone, which condenses with phenol to produce2,2-bis-(4-hydroxyphenyl)-propane, commonly known as bisphenol A.Another preferred aliphatic ketone is hexafluoroacetone, which reactswith two moles of phenol to produce2,2-bis-(4-hydroxyphenyl)-hexafluoropropane (bisphenol AF).

A preferred class of ketones has at least one hydrocarbyl groupcontaining an aryl group, for example, a phenyl, tolyl, naphthyl, xylylor 4-hydroxyphenyl group.

Other preferred ketones include those in which the hydrocarbon radicalsconnected to the carbonyl groups of the ketone is in a cycloaliphaticgroup. Examples of specific preferred ketones include 9-fluorenone,cyclohexanone, 3,3,5-trimethylcyclohexanone, indanone, indenone,anthraquinone and the like.

Most preferred ketones include 9-fluorenone, benzophenone, acetone,acetophenone, 4-hydroxyacetophenone and 4,4'-dihydroxybenzophenone. Mostpreferably, the process of this invention is used to make bisphenol A byreaction of phenol with acetone or to make9,9-bis-(4-hydroxyphenyl)fluorene (BHPF) by reaction of phenol with9-fluorenone.

The process of this invention can also be used for the condensation ofphenols with aldehydes, for example, with formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde or higher homologues of the formula RCHO,wherein R is alkyl of 1-20 carbon atoms. The condensation of two molesof phenol with one mole of formaldehyde producesbis-(4-hydroxyphenyl)methane, also known as Bisphenol F.

It will be understood that dialdehydes and ketoaldehdyes, for example,glyoxal, phenylglyoxal or pyruvic aldehyde, can also be used.

The products are generally geminal bisphenols, that is, compounds havingone or more single carbon atoms to which are attached nuclei of twophenolic moieties. This single carbon atom corresponds to the carbonylcarbon of the ketone or aldehyde reactant. In the case of startingmaterials, containing more than one aldehyde or ketone carbonyl, theproduct will contain more than one geminal bisphenolic moiety. Forexample, the condensate from acetyl acetone and phenol is2,2,4,4-tetrakis-(hydroxyphenyl)pentane and the condensate frombenzoylacetone is 2,2,4,4-tetrakis-(hydroxyphenyl)-4-phenylbutane.

The mercaptosulfonic acid catalyst is any species, whether soluble orinsoluble in the reaction mixture, containing at least one thiol (SH)group and at least one sulfonic acid (SO₃ H) group, including any groupwhich can be converted to a sulfonic acid group under the reactionconditions used.

In the specification and claims, the soluble mercaptosulfonic acidmoiety is represented by the formula

    (HS).sub.a --θ--(SO.sub.3 H).sub.b

wherein θ is an alkylene, cycloaliphatic, arylene, alkylenearylene,alkylenecycloaliphatic, alkylenearyl, heterocyclic oralkyleneheterocyclic residue and each of a and b is independently aninteger from 1 to about 20.

"Soluble mercaptosulfonic acid," as used in the specification andclaims, means a compound which has some solubility in the reactionmixture and which can be removed from the mixture, at the end of thereaction, by extraction, ion-exchange, precipitation, absorption, etc.

"Insoluble mercaptosulfonic acid," as used in the specification andclaims, means a material, which is insoluble in the reaction mixture.These materials are generally polymeric organic resins, orcatalytically-active compounds, bonded to an inorganic support.

When θ is alkylene, the alkylene can be of 2 to up to about 20 carbonatoms, including straight and branched chain alkylene moieties,corresponding heterochain moieties and alkylene substituted with inertsubstituents. Inert substituents include, for example, alkoxy, alkenyl,alkynyl, halo, nitro, aryl, etc.

Representative mercaptoalkanesulfonic acids include, but are not limitedto, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid,4-mercaptobutanesulfonic acid, 4-mercaptopentanesulfonic acid,3-mercapto-2,2-dimethylpropanesulfonic acid,2,3-dimercaptopropanesulfonic acid, mercaptopropane-2,3-disulfonic acid,2-benzyl-4-mercaptobutanesulfonic acid, 5-mercaptopentanesulfonic acidor the like. Most preferred among this group of catalysts are3-mercaptopropanesulfonic acid and 4-mercaptobutanesulfonic acids.

The types of mercaptoalkanesulfonic acids which are useable areexemplified by the following compounds of Formula I: ##STR7## wherein Qis an inert substituent and Y is an optional hetero element, e.g. O,N--Q or S. Q is H, hydrocarbyl, halo, carboxy, sulfonyl, etc., asdescribed above for inert substituents on the phenol, ketone or aldehydestarting materials. More than one Q may optionally be present. The Qsubstituent can be at any position on the chain and more than one Q canbe present. As set forth in the general formula for the solublecatalysts, more than one SH or sulfonic acid function are optionallypresent in the catalyst.

Compounds of Formula I(a) are included within the generic formula

    HS (CH.sub.2).sub.y CH (Q)(CH.sub.2).sub.z SO.sub.3 H

wherein y is an integer from 0 to about 20, z is an integer from 0 toabout 20, Q is an optional inert substituent and y+z≧1, up to a maximumof about 40.

Compounds of Formula I(b) are included within the generic formula

    HS (CH.sub.2).sub.y --Y--(CH.sub.2).sub.z SO.sub.3 H,

wherein one or more inert substituents, Q, can be attached at any pointalong the carbon chain; wherein Y is a heteroelement, e.g. --S--; eachof y and z is at least 1 and y+z≧2, up to a maximum of about 40.Preferred linear mercaptoalkanesulfonic acids are those in which thedistance between the mercapto and sulfonic acid functions are less thanabout 20 atoms, including both carbon and heteroatoms. Compounds ofFormula I(b) can also have more than one SH and/or more than onesulfonic acid function.

Compounds of Formula I(c) are included within the formula ##STR8##wherein y and z are as above.

Mercaptosulfonic acid precursors can also be used as catalysts, byconversion to active mercaptosulfonic acid catalysts in the reactionmixtures. For example, a precursor alkali metal sulfonate salt can beneutralized with a mineral acid to produce a free sulfonic acid.Sulfonate ester precursors can be hydrolyzed by treatment with a strongbase, e.g. sodium or potassium hydroxide, and thus converted to acorresponding alkali metal salt. A further precursor of sulfonic acidsfor the practice of this invention, is a sulfonyl halide group, whichcan readily converted to a corresponding sulfonic acid.

Mercaptosulfonic acids can be prepared from correspondinghaloalkanesulfonic acids by reaction with an alkali metal mercaptide,for example,

    X-alk-SO.sub.3 H+NaSH→HS-alk-SO.sub.3 H+NaX

wherein X is Cl, Br or I and alk is alkylene, generally in accordancewith Ellis et al., "The Preparation and Properties of a Double Series ofAliphatic Mercaptans," J. Am. Chem. Soc., vol. 54 (1932), pages1674-1687.

Alternatively, treatment of a haloalkanesulfonic acid with an alkalimetal thioacetate, followed by hydrolysis, can be used to preparemercaptoalkanesulfonic acids.

Another route to mercaptosulfonic acids is by converting halides to acorresponding thiouronium salt, which is hydrolyzed with a strong base,as follows: ##STR9## generally according to Schramm et al., "TheSynthesis of mercaptoalkanesulfonic Acids," J. Am. Chem. Soc., vol. 77(1955), pages 6231-6233.

Hydroxyalkanesulfonic acids can also be converted to the correspondingmercaptoalkanesulfonic acid by reaction with thiourea and HBr/HCl toproduce a thiouronium salt, which is hydrolyzed using a strong base.See, Frank et al., "The Preparation of Mercaptans from Alcohols," J. Am.Chem. Soc., vol. 67 (1946), pages 2103-2104.

Higher mercaptoalkanesulfonic acids can be prepared from higherolefinsulfonic acids, e.g. oleylsulfonic acid, by adding hydrogensulfide across the olefinic bond. Alternatively, the olefinic bond of anolefinic sulfonic acid can be halogenated, e.g., chlorinated, and thehalogen moiety replaced by a mercapto function, as above.

Mercaptoalkanesulfonic acids can also be made from correspondingsultones, e.g., 1,4-butanesultone, in accordance with Chem. Abs.,90:86742m (1979); R. Fischer, "Propanesultone," Ind. Eng. Chem., vol. 56(1964), pages 41-45; or A. Mustafa, "The Chemistry of Sultones andSultams," Chemical Reviews, vol. 54 (1954), pages 195-223.

When --θ-- is arylene, the sulfonic acid and mercapto moieties areattached directly to an aromatic ring. Representative aromaticmercaptosulfonic acids include 2-mercaptobenzenesulfonic acid,3-mercaptobenzenesulfonic acid, 4-mercaptobenzenesulfonic acid,2-mercaptonaphthalenesulfonic acid or the like. The aromatic residuescan be substituted with substituents, e.g., H, alkyl, alkenyl, alkynyl,aryl, halo, alkoxy, aryloxy (Q, above), which are inert under thereaction conditions. The active catalysts can contain more than one SHand/or more than one sulfonic acid function in each molecule.

Cycloaliphatic residues include those of cyclohexane, cyclopentane andcycloheptane; the aliphatic ring of indane, tetralin orbenzocycloheptane, and the like. Representative cycloaliphaticmercaptosulfonic acids include, but are not limited to,2-mercaptocyclohexanesulfonic acid, 2-mercaptocyclopentanesulfonic acid,3-mercaptocyclohexanesulfonic acid, 3-mercaptocyclopentanesulfonic acidand the like. The cycloaliphatic rings can also be substituted withinert substituents and can contain more than one SH group and/or morethan one sulfonic acid group.

Representative alkylenecycloaliphatic mercaptosulfonic acid compoundscan be represented by the following formulas: ##STR10## wherein y and zare integers of 0 to about 20; Q is an optional inert substituentselected from alkyl, aryl, halo, alkoxy or aryloxy and y+z≧1. Typicalcompounds include (mercaptomethyl)cyclohexanesulfonic acid and(mercaptomethyl)(sulfomethyl)cyclohexane.

Typical alkylenearyl mercaptosulfonic acids can be represented by theformulas: ##STR11## wherein x, y and Q are as above and x+y≧1.

A typical compound of this group, (mercaptomethyl)benzene-sulfonic acid,can be prepared from a corresponding chloromethyl- orbromomethylbenzenesulfonic acid.

Oligomers from vinylsulfonic acid can provide soluble materials,containing large numbers of mercapto and sulfonic acid groups. This typeof soluble catalyst can be prepared from oligomers containingvinylsulfonic acid units, half of which can be converted tochlorosulfonyl units and reduced to mercapto units in accordance withthe following reaction scheme: ##STR12##

Another type of oligomeric catalysts, containing a multiplicity ofmercapto and sulfonic acid units, can be prepared from propenesultone.Propenesultone is prepared as described by G. Manecke et al., Chem. Abs.53:2083c (1959), Helberger et al., DE 1,146,870 and Chem. Abs. 59:11259(1963). The sultone ring of the polymer can be opened, generally asabove, to furnish mercaptosulfonic acid oligomers, containing aplurality of mercapto and sulfonic acid units.

In addition, oligomers containing a plurality of mercaptosulfonic acidfunctions can be prepared from oligomers of 4-allyl-1,4-butanesultone.The monomer is prepared as described for 4-benzyl-1,4-butanesultone,using allyl chloride instead of benzyl chloride.4,4-Diallyl-1,4-butanesultone can be prepared by addition of a secondallyl group.

Other catalytically active mercaptosulfonic acid oligomers can beprepared from allyl vinylsulfonate (CH═CHSO₂ OCH₂ CH═CH₂), which ispolymerized to form a corresponding sultone-containing polymer inaccordance with E. Goethals, "Synthesis and Polymerization of AllylVinyl Sulfonate," Polymer Letters, vol. 4 (1966), pages 691-693. Theresulting polymer, containing sultone groups is treated with a reactivethiolate to open the sultone rings and produce mercaptoalkyl sulfonatepolymers.

The conversions can be represented by the equation: ##STR13##

Similar catalytically-active solid oligomers can be prepared fromoligomers of allyl allylsulfonate (CH₂ ═CHCH₂ SO₂ OCH₂ CH═CH₂), whichcan be polymerized in accordance with E. Goethals et al.,"Polymerization and Copolymerization of Allyl Allyl Sulfonate," J.Macromol. Sci.--Chem., vol. A5 (1971), pages 63-72. The oligomers areconverted to mercaptosulfonic acid functional materials by acorresponding ring opening reaction.

The conversion can be represented by the equation: ##STR14##

Heterocyclic residues advantageously include cyclic residues, containingN, O, or S. These will generally correspond to aromatic compounds, forexample, residues from pyridine, thiophene, quinoline, phenanthridine,and the like, as well the corresponding partially or fully hydrogenatedcompounds. Alkyleneheterocyclic residues otherwise correspond toaromatic residues of the same configuration, as do alkyl heterocyclicresidues, as well as corresponding fully or partially hydrogenatedcompounds.

Preferred soluble mercaptosulfonic acids are compounds in which themercaptan and sulfonic acid functions are separated by a chain of about2 to about 10 atoms, whether the chain or linker arm is in an alkylenegroup or incorporated in an aromatic, cycloaliphatic or heterocyclicring, whether or not the chain includes heteroelements, and whether ornot the mercapto and sulfonic acid functions are attached directly orindirectly to the ring structures. Preferred soluble catalysts for thepractice of this invention are mercaptosulfonic acids in which a and bare independently 1 from to about 4. More preferably, a and b areindependently 1 or 2. Most preferred are mercaptosulfonic acids,containing mercapto and sulfonic acid functions in a 1:1 molar ratio,that is a and b are each 1, more particularly 3-mercaptopropanesulfonicacid and 4-mercaptobutanesulfonic acid.

When the mercaptosulfonic acid is insoluble, the heterogeneous catalystcomprises a catalytically-active species represented by Formula II:##STR15## in which each of a and b is independently an integer from 1 toabout 20, θ' is an alkylene, cycloaliphatic, arylene, alkylenearylene,alkylenecycloaliphatic, alkylenearyl, heterocyclic oralkyleneheterocyclic residue, L is an optional linking group and -- is abond, which catalytically-active species is attached by the bond -- toan insoluble organic or inorganic support;

or a catalytically-active species represented by Formula III: ##STR16##wherein θ" is an alkylene, arylene, cycloaliphatic, alkylenearylene,alkylenecycloaliphatic, alkylenearyl, heterocyclic oralkyleneheterocyclic residue; a and b are independently selected fromintegers from 1 to about 20; L' is an optional linking group and -- is abond.

Catalytically-active materials of Formula II are generally derived frompolymers of ethylenic monomers, wherein the insoluble organic support isthe main chain of a resulting polymer and --L-- is a covalent bond or alinking group. This type of polymer will include unit structuresrepresented by the general formula ##STR17##

Preferably, the catalytically-active materials will include those havingfrom 1 to about 4 of each of mercapto and sulfonic acid groups per θ'.More preferably, the catalytically-active materials will include thosehaving 1 or 2 of each of mercapto and sulfonic acid groups per θ'. Mostpreferably, the catalytically-active materials contain 1:1 ratios ofmercapto and sulfonic acid functions and will correspond to the generalformula ##STR18##

Exemplary polymers, made from ethylenically unsaturated monomers andwhich can be used as carriers for the catalytically-active species,include, but are not limited to:

    ______________________________________                                        L             θ'    Monomer(s)                                          ______________________________________                                        --            phenyl      styrene                                               --CH.sub.2 -- phenyl allylbenzene                                             --O-- phenyl phenyl vinyl ether                                               --COO-- alkyl, aryl acrylic esters                                            --OCO-- alkyl, aryl vinyl esters                                              --(CH.sub.2).sub.r -- alkenyl α,ω-diolefins                       r = 4-20                                                                      --NH-- alkyl, aryl vinylamines                                                --CONH-- alkyl, aryl acrylamides                                              --NHCOO-- alkyl, aryl vinylurethanes                                          -- alkylphenyl vinyltoluene                                                   -- phenyl α-methylstyrene                                               --S-- phenyl phenyl vinyl ether                                               --SO.sub.2 -- aryl vinyl aryl sulfones                                        --SO-- aryl vinyl aryl                                                          sulfoxides                                                                  --NSO.sub.2 -- aryl aryl sulfonamide                                        ______________________________________                                    

The linking groups, --L--, can accordingly include alkylene, a covalentbond, oxycarbonyl, carbonyloxy, oxy, ureido, amido, amino, thio(sulfur), sulfono or sulfoxo. Preferred linking groups include acovalent bond, methylene, sulfur or oxygen, more particularly a covalentbond joining a phenyl ring to a carbon backbone in polystyrene orpolystyrene derivatives, containing each of SH and SO₃ H functions insingle monomeric units of polystyrene.

One type of novel catalytically-active polystyrene resins, includes unitstructures represented by Formula IV ##STR19## wherein B is a bridginggroup, R and R¹ are independently selected from H, alkyl or aryl,--C_(n) H_(2n) -- is straight or branched chain alkylene and n is aninteger from 0 to about 20.

The bridging group B, can be selected from alkylene, generally as above.Alkyl and aryl are defined above.

Polystyrene resins of Formula IV can be made by the steps of (a)reacting a haloalkystyrene polymer with a lithiated sultone, (b)treating a resulting sultone-functionalized polymer with a reactivethiolate and (c) acidifying the resulting intermediate to produce apolymer containing (mercaptosulfoalkyl)styrene units.

Haloalkylstyrene polymers include, but are not limited topoly(chloromethylstyrene), poly(bromomethylstyrene),poly(bromopropylstyrene), poly(bromopentyl)styrene or the like.including homopolymers and copolymers, whether made by polymerization ofhaloalkylstyrene monomers or haloalkylation of polystyrene resins.Representative starting materials can be made by copolymerization ofvinylbenzyl chloride or vinylbenzyl bromide with styrene. Eitherstarting material can be crosslinked with divinylbenzene or similarcrosslinking monomers. The polymers can contain other monomers, e.g.,styrene, α-methylstyrene, acrylonitrile, butadiene, maleic anhydride,ethylene or propylene.

The haloalkylated polymers will advantageously contain from about 0.5meq/g to about 10 meq/g of halomethyl groups. Halomethylated orhaloalkylated polymers normally comprise mixtures of polymers,substituted in the ortho-, meta- and para-positions.

Poly(chloromethylstyrene), containing about 2-5 meq/g of chlorine, is apreferred starting material.

The reaction sequence described above can be performed utilizing avariety of chloromethylated or bromomethylated styrene polymers orcopolymers. In particular, crosslinked halomethylatedstyrene/divinylbenzene co-polymers in various forms, e.g. microporous ormacroporous beads, powders, etc., can be functionalized to provide thecorresponding mercaptosulfonic acid polymers.

In the case of all the polymer based catalysts utilization of thefunctionalized styrene or other polymers in bead form may advantageouslysimplify workup procedures during preparation and provide for morefacile implementation in catalyst applications. Beads are suitably ofany size through which effective flow and contact is achieved. Physicalforms including powders, beads, extruded shapes, macroporous andmicroporous configuration are, however, suitably used in the practice ofthe invention. In general smaller size provides more surface area forcontact, but larger size permits greater flow through a bed. Optimizingthese factors is within the skill in the art.

Reactive thiolates advantageously include, but are not limited to,sodium thioacetate, potassium thioacetate, ammonium thioacetate andlithium thioacetate and the corresponding hydrosulfides. Of these,lithium, sodium or potassium thioacetate is preferred.

When conversion to a mercapto function is done through a thioureaintermediate, the thioureas are advantageously selected from thiourea,N-methylthiourea, N-ethylthiourea, N-phenylthiourea or the like. Inanother alternative procedure, sodium thiosulfate can be used.

A preferred species of catalytically-active polystyrene resin is made byreacting poly(chloromethyl)styrene with lithiated 1,4-butanesultone toproduce an intermediate sultone, represented by the structural unitformula: ##STR20##

The resulting polymer contains (ε-mercapto-β-sulfo-pentyl)styrene units,that is, n in Formula IV is 2 and B is --CH₂ --.

Most preferably, this type of resin is made from a slightly crosslinkedpolystyrene; the resulting catalytically active material is designatedas PMBSA-MER.

Another type of catalytically-active polystyrene resins can be preparedby the steps of:

(a) alkylating a polystyrene with an alkenyl halide of the formulaRC(R¹)═C(R²)C_(m) H_(2m) CH(R³)X, wherein each of R, R¹, R² and R³ is H,alkyl or aryl; m is 0 to about 20 and X is F, Cl, Br or I to produce ahaloalkyl polystyrene;

(b) sulfonating the resulting haloalkylpolystyrene to produce anintermediate having sulfo functional groups;

(c) optionally converting the sulfo functional groups to a sodium orpotassium sulfonate function;

(d) thiolating the thus-produced sulfostyrene intermediate by reactingthe halo function with a reactive thiolate to produce a correspondingmercapto function or precursor thereof and (e) optionally hydrolyzingthe thus-thiolated intermediate with an acid or base when the thiolatedgroup so requires; and

(f) optionally acidifying (if so required) to produce the sulfonic acidfunction.

This process can be represented broadly by the reaction sequence:##STR21## to produce intermediate haloalkyl sulfonated styrene polymers,of which halo functions are converted to mercapto functions to producethe following types of products of Formula V: ##STR22##

Alkenyl halides optionally contain aryl and alkyl substituents, asdefined above. Representative alkenyl halides, useful for preparing thecatalytically-active polymers, include, but are not limited to, allylchloride, allyl bromide, allyl iodide, methallyl chloride, methallylbromide, crotyl chloride, crotyl bromide, 4-bromo-1-butene,5-bromo-1-butene, 6-bromo-1-hexene or higher chloro or bromoalkenes.Preferably, the alkenyl halides are allylic halides, represented by theformula RC(R¹)═C(R²)CH(R³)X. Most preferably, the alkenyl halide is5-bromo-1-pentene, 11-bromo-1-undecene or allyl bromide.

A particularly preferred product thus made can be characterized by theformula, in the case of a product from 5-bromo-1-pentene: ##STR23## or,when the halide is allyl bromide or allyl chloride, by the formula:##STR24##

Reactive thiolates are as defined above. Most preferably, the reactivethiolate is an alkali metal thioacetate or hydrosulfide.

By varying the choice of starting bromoalkene (or other haloalkene) usedin the alkylation step of the process, the basic procedure describedabove can also be used to prepare a variety of catalysts with varyingchain lengths between the mercaptan and sulfonic acid moieties. A numberof catalysts with different amounts of mercaptosulfonic acid sites,depending upon the degree of functionalization in the alkylation andsulfonation steps in the process, and structural relationships betweenthe mercaptan and sulfonic acid sites, depending upon the choice ofbromo- or chloroalkylating agent, can accordingly be made.

Preferred catalytically-active species of Formula V are those derivedfrom polystyrenes, treated with 5-bromo-1-pentene, 11-bromo-1-undeceneor an allylic halide of the formula RCH═CH₂ CH₂ X, wherein R is H oralkyl of 1-5 carbon atoms.

In another aspect, this invention relates to novel[(mercaptoalkyl)(sulfo)phenylalkyl] sulfonated polystyrene catalysts,made by a process comprising the steps of:

(a) alkylating a haloalkylated polystyrene with a haloalkylarylenecompound to produce an intermediate haloalkylpolystyrene having[(haloalkyl)phenylalkyl] styrene units;

(b) sulfonating the thus-produced haloalkylpolystyrene intermediate toproduce an intermediate having sulfo functional groups;

(c) optionally converting the sulfo functional groups to correspondingalkali metal salts;

(d) thiolating the thus-produced sulfostyrene intermediate by reactingthe halo function with a reactive thiolate to produce a correspondingmercapto function or precursor thereof and (e) optionally hydrolyzingthe thus-thiolated intermediate with an acid or base when the thiolatedgroup so requires; and

(f) optionally acidifying (if so required) to produce the sulfonic acidfunction.

This process produces polymers having repeating units of the formula:##STR25## wherein n is preferably an integer from 0 to 10, morepreferably 2 or 3.

A representative member of this series of polymers, designated asDPMSA-XE3C is made from choromethylstyrene polymer and3-bromopropylbenzene, in accordance with the following reactionsequence: ##STR26##

The haloalkyl polystyrene starting materials can advantageously beselected from chloromethylated polystyrenes, bromomethylatedpolystyrenes, chloroethylated polystyrenes, iodoethylated polystyrenesor the like, generally as above, preferably the halomethylatedpolystyrenes. Those skilled in the art recognize that selectivitydecreases with haloalkyl groups on aryl rings which groups have similarselectivity.

The haloalkylaryene compound can conveniently be selected fromchlorobenzene, (chloromethyl)benzene, (chloroethyl)benzene,(chloropropyl)benzene, (chlorobutyl)benzene, as well as thecorresponding fluoro, bromo and iodo analogues. Representative examplesinclude (2-chloroethyl)benzene, (2-bromoethyl)benzene,(2-iodoethyl)benzene, 1-chloro-3-phenylpropane, 1-bromo-3-phenylpropane,and 1-iodo-3-phenylpropane. The bromo compounds are preferred.

The alkylation is conveniently carried out in the presence of aFriedel-Crafts catalyst, of which aluminum trichloride, aluminumbromide, boron trifluoride, hydrogen fluoride, phosphoric acid, zincchloride, titanium chloride, ethylaluminum dichloride and stannicchloride are representative. A preferred catalyst is aluminum chloridein nitromethane or nitrobenzene, as disclosed by A. Warshawsky et al.,"Functionalization of Polystyrene. I. Alkylation with Substituted BenzylHalide and Benzyl Alcohol Compounds," J. Org. Chem., vol. 43 (1978),pages 3151-3157.

Conveniently, after alkylation, unreacted haloalkylbenzene, solvent andcatalyst in admixture are removed from the alkylated polystyrene bymeans within the art such as filtration. Advantageously, the admixtureis recycled for reaction with additional haloalkyl polystyrene. Thealkylated polystyrene is optionally washed with a solvent such asdichloromethane and optionally dried.

The resulting alkylated polystyrene is sulfonated using chlorosulfonicacid, oleum or other known sulfonating agents. Prior to conversion ofthe halo moiety to the mercapto moiety, it is convenient to convert thesulfo moieties to corresponding alkali metal salts. Chlorosulfonic acid,sulfuric acid or sulfur trioxide is conveniently used in an amountsufficient to achieve a predetermined or desirable degree ofsulfonation, advantageously to avoid unnecessary workup, in an amountnot in large excess of the sufficient amount which varies with eachresin but is determined without undue experimentation. The advantages oflower reaction temperatures are greater with chlorosulfonic acid.

The thiolating reagents are conveniently selected from those disclosedabove. Sodium thioacetate is preferred. Excess sodium hydrosulfide isoptionally used for thiolation. Hydrolysis is then unnecessary since athio group rather than a thioacetate is formed. The intermediatethiolated compound is, if necessary, acidified with a strong acid toconvert sulfonate salt moieties to corresponding sulfonic acid moieties.Advantageously, a mineral acid is used, as above.

In an alternate embodiment, the process comprises:

(a) alkylating a polystyrene resin with a halomethyl haloalkylarylenecompound to produce an intermediate having [(haloalkyl)phenylalkyl]styrene units,

(b) sulfonating the thus-produced intermediate to produce anintermediate having sulfo functional groups;

(c) optionally converting the sulfo functions to corresponding alkalimetal salts;

(d) thiolating the thus-produced sulfostyrene intermediate by reactingthe halo function with a reactive thiolate to produce a correspondingmercapto function or precursor thereof and (e) optionally hydrolyzingthe thus-thiolated intermediate with an acid or base when the thiolatedgroup so requires; and

(f) optionally acidifying (if so required) to produce the sulfonic acidfunction.

Illustrative of this reaction is the following sequence: ##STR27##

The alkylating step is performed as in the preceding process optionallyin a solvent such as chloroform, 1,2-dichloroethane, dichloromethane,1,2-dichloropropane, preferably a solvent which swells polystyrene (e.g.styrene/divinylbenzene copolymer beads). The alkylating agent is anyhalomethyl haloalkylarylene preferably wherein the alkyl group has from0 to about 10 carbon atoms. The arylene group preferably has from 6 toabout 14 carbon atoms.

It is within the skill in the art to select halomethyl haloalkylarylenesin which the haloalkyl and halomethyl groups have activitiessufficiently different to achieve the desired result.

Representative halomethyl haloalkylarylene compounds include(2-bromoethyl)benzylchloride and (3-bromopropyl)benzylchloride.Chloromethyl haloalkylarlenes are conveniently prepared by means withinthe skill in the art such as described by Selva et al., Synthesis, 1991,1003-1004 wherein haloalkylarylenes are reacted with formaldehyde inacid (e.g. sulfuric or hydrochloric) in the presence of a quaternaryammonium phase transfer catalyst. Chloromethylation can also beperformed using zinc chloride and paraformaldehyde in accordance withthe method described by Daren in U.S. Pat. No. 4,967,026. Alternatively,chloromethyl ethers are used to chloromethylate a haloalkyl arylene bymethods similar to that taught by Raley in U.S. Pat. No. 3,311,602, byShinka, et al. J. Poly. Sci. Polym. Lett. Ed. 14(1), 1-3 (1976), and byShigeo, et al. Chem. Abstr. 72:32290 (1970), or by other means withinthe skill in the art.

In another aspect, hydrohalogenating agents such as HBr are added toalkenyl arylenes such as styrene under radical forming conditions suchas taught by Martan in U.S. Pat. No. 4,228,106 or Plesmid in U.S. Pat.No. 3,321,536 which patents are incorporated herein by reference intheir entireties. In an extension of these works, vinylbenzyl chlorideis hydrobrominated by this method.

The sulfonation and thiolation steps are as described for the previousprocess.

In addition to the methods disclosed above, a variety of other methodsare also available for preparing the haloalkyl-functionalizedpolystyrene resins which are precursors to the mercaptosulfonic acidpolymer catalysts. Representative approaches for preparing thehaloalkylated polystyrene resins include (but are not limited to) thosedescribed or discussed by: a) P. C. Reeves and M. S. Chiles, "PhaseTransfer Catalysts Anchored to Polystyrene," Tetrahedron Letters (1979),pages 3367-3370 b) M. Tomoi, et. al., "Novel Synthesis ofSpacer-Modified Polymer Supports and Activity of Phase-TransferCatalysts Derived from the Polymer Supports," J. Polymer. Sci. PolymerChem. Ed., vol. 20 (1982), pages 3015-3019 c) M. J. Farrall and J. M. J.Frechet, "Bromination and Lithiation: Two Important Steps in theFunctionalization of Polystyrene Resins," J. Org. Chem., vol. 41 (1976),pages 3877-3882 d) S. P. McManus and R. D. Olinger, "Reactions of CyclicHalonium Ions and Alkylene Dihalides with Polystyryllithium. Preparationof Haloalkylated Polystyrene," J. Org. Chem., vol. 45 (1980), pages2717-2719 e) M. Haratake, et. al. "Sorption of Phenols on Anion-ExchangeResins Having, ω-Oxoalkyl or ω--Hydroxyalkyl Spacer," AnalyticalSciences, vol. 4 (1988), pages 591-594 f) M. Gauthier and A. Eisenberg,"Alkylated Styrene Ionomers with Variable Length Spacers. I. Synthesis,"J. Polymer Sci.: Part A: Polymer Chem., vol. 28 (1990), pages 1549-1568g) P. Tundo, "Easy and Economical Synthesis of Widely Porous Resins;Very Efficient Supports for Immobilized Phase-Transfer Catalysts,"Synthesis (1978), pages 315-316 h) Tachikawa, et. al. "Process for theProduction of Silanes" (U.S. Pat. No. 4,725,420) i) G. Zheng, et. al."Synthesis of Bromoalkylated Crosslinked Polystyrene," Xinan ShifanDaxue Xuebao, Ziran Kexueban, vol. 2 (1986) pages 68-70 j) M. L.Hallensleben, "Preparation of Poly(p-(ω--lithiumalkyl)styrenes) andTheir Use as Polymer Metalating Agents," Angew. Makromol. Chem., vol. 31(1973), pages 147-159 k) F. Doscher, et. al., "Synthesis ofSulfoalkylated Styrene-Divinylbenzene Copolymers," Makromol. Chem.,Rapid Commun., vol. 1 (1980), pages 297-302. It is to be understood thata haloalkylated polystyrene resin prepared in a manner such as thatdescribed in the above references could be further functionalized by thesulfonation and thiolation procedures previously described to provide amercaptosulfonic acid polymer catalyst.

Other representative references on methods for polymer modification orfor uses of functional polymers include Akelah et al., "Application ofFunctionalized Polymers in Organic Synthesis," Chem. Rev., vol. 81(1981), pages 557-587; Frechet et al., "Functionalization of CrosslinkedPolystyrene Resins by Chemical Modification: A Review," in "Chemistryand Properties of Crosslinked Polymers," S. Labana, ed., Academic Press,New York (1977), pages 59-83; and Marechal, "Chemical Modification ofSynthetic Polymers," in "Comprehensive Polymer Science," vol. 6, Allen,ed., Pergamon Press, New York, pages 1-47.

Catalysts derived from polystyrenes will advantageously contain fromabout 0.2 to about 5 meq of mercapto/sulfonic acid functionality per g,most preferably from about 2 to about 4 meq/g.

It will be understood that polymers, containing large amounts ofmercapto/sulfonic acid functionality on a given carrier, pendant from ahydrocarbon chain, can be prepared by grafting vinylsulfonic acid,propenesultone, or the like, to the pendant carrier function, andconverting the grafted polymer to materials having mercapto/sulfonicacid functionality.

Catalytically-active polymers in which--is an ionic bond canadvantageously be prepared from ion-exchange resins and reactivecompounds, containing both mercapto and sulfonic acid functions.

For example a strongly basic ion-exchange resin such as poly(vinylbenzylamine) can be reacted with a compound such as4-mercapto-1,2-butanesulfonic acid to produce catalytically-activematerial as represented by the equation: ##STR28##

Representative strongly basic ion-exchange resins include Dowex™1X2-400, Amberlyst™ A-21, Dowex™ WGR-1, DoWex™ WGR-2 and Dowex™ MSA-1.The WGR resins are polypropyleneimines, conveniently obtained bycondensation of epichlorohydrin with ammonia.

Catalytically-active materials can also advantageously be prepared froman acidic ion-exchange resin, e.g. sulfonated polystyrene by reactionwith an aminomercaptosulfonic acid, e.g. 2-mercapto-4-aminobenzenesulfonic acid, as represented by the equation: ##STR29##

Representative strongly acidic cation-exchange resins include Dowex™50X2-400, Amberlyst™ A-21 and Dowex™ MSC-1.

In addition to the use of polymers from ethylenically unsaturatedmonomers, including copolymers, as insoluble supports for thecatalytically-active species, the catalytically-active species can beattached to an inorganic support, e.g. a mineral, such as silica,alumina, aluminosilicates or glass, through the linking group --L--. Arepresentative case is that wherein the linking group is --OSiO-- or##STR30## most preferably, --OSiO--.

Catalytically-active species of Formula III will conveniently beincorporated in the backbone of condensation polymers, e.g. polyesters,polyamides, polycarbonates, polyurethanes, polysiloxanes, polyamines,polyethers, polyketones, polysulfones, polysulfoxides and the like. Thedivalent linking group, --L'--, can be selected from such structures aspolyoxy(alk-di-yl), polyoxy(ar-di-yl), dioxy(alkar-di-yl),polyoxy(aralk-di-yl), polythio(alk-di-yl), polythio(aralk-di-yl),polythio-(ar-di-yl), polythio(alkar-di-yl), polythio(aralk-di-yl),polyamido(alk-di-yl), polyamido(ar-di-yl), polyamido-(aralk-di-yl),polycarbonyloxy(alk-di-yl), polycarbonyloxy(ar-di-yl),polycarbonyloxy(alkar-di-yl), polycarbonyloxy(aralk-di-yl)polycarbonyldioxy(alk-di-yl), polycarbonyldioxy(ar-di-yl),polycarbonyldioxy(alkar-di-yl), polycarbonyldioxy(aralk-di-yl),polyamino(alk-di-yl), polyamino(ar-di-yl), polyamino(alkar-di-yl),polyamino(aralk-di-yl), polycyclimido(ar-di-yl),polycyclimido(alkar-di-yl), polycyclimido(aralk-di-yl),polycarbonyl(alk-di-yl), polycarbonyl(ar-di-yl),polycarbonyl-(alkar-di-yl), polycarbonyl(aralk-di-yl),polyimido(alk-di-yl), polyimido(ar-di-yl), polyimido(alkar-di-yl),polyimido(aralk-di-yl), polyureylene(alk-di-yl), polyureylene(ar-di-yl),polyureylene(aralk-di-yl), polyureylene alkar-di-yl),polycarboxamideoxy(alk-di-yl), polycarboxamideoxy(ar-di-yl),polycarboxamideoxy(alkar-di-yl), polycarboxamideoxy(alkar-di-yl),polycarboxamideoxy(aralk-di-yl), ar-di-yl, alkaryl-di-yl, aralkyl-di-yland alkenoic-di-yl. Preferred divalent linking groups, --L'--, includedi(carbonyloxy)hydrocarbylene, siloxy, dicarboxamidohydrocarbylene,di(oxycarbonyl)hydrocarbylene, dithiohydrocarbylene, and hydrocarbylenegroups containing aromatic rings.

During batch processing, the mercaptosulfonic acid catalyst is suitablypresent in an amount sufficient to enable condensation of the phenolwith the ketone/aldehyde in a reasonable time. Preferably, the amount ofmercaptosulfonic acid ranges from about 0.01 equivalents to about 2.0equivalents of catalyst per 1.00 equivalents of the ketone/aldehyde.More preferably, the amount of mercaptosulfonic acid catalyst is fromabout 0.02 to about 1.0 equivalent of mercaptosulfonic acid perequivalents of aldehyde/ketone. Most preferably, the reaction mixturewill contain from about 0.03 to about 1.0 equivalent of mercaptosulfonicacid per equivalents of aldehyde or ketone under batch processing.

When ketone/aldehyde is added over the course of a reaction (e.g. acontinuous reaction) the previously stated preferred amounts refer tototal catalyst and reactants added rather than catalyst present in areaction mixture at a given moment. Those skilled in the art recognizethat when a reactant is added incrementally or continuously, there isoften a large excess of catalyst. The ratio of catalyst toketone/aldehyde in the reaction mixture is advantageously greater thanone, conveniently on the order of 20 equivalents to 1 equivalent.

Due to the high activity of the mercaptosulfonic acid catalysts, goodreaction rates and high selectivity can be obtained at temperaturesbelow the melting point of phenol. The phenol reactant canadvantageously be kept in the liquid state by addition of solvents,e.g., water, methylene chloride, diphenylmethane, etc. Low temperaturereactions are often particularly advantageous, because the productdiphenolic compounds crystallize in the reaction mixture and becauselower reaction temperatures favor higher selectivity toward4,4-bisphenolic products.

The reaction temperature will accordingly advantageously be selected inthe range from about 0° C. to about 100° C., preferably from about 15°C. to about 60° C. Temperature ranges can be chosen by routineexperimentation, depending upon the ketone/aldehyde and phenol feeds.

When excess phenolic compound is used as solvent, the temperature forthe condensation is advantageously selected so that the phenol is in theliquid state. In the case of high-melting phenols, e.g. those meltingabove about 180° C., the use of an inert solvent is preferred.Diphenylmethane has been found to be particularly useful for thispurpose. Other useable inert solvents include, but are not limited to,the xylenes, mesitylene, the durenes, fluorobenzene, toluene,cyclohexane, chlorobenzene, halogenated aliphatic hydrocarbons andalkylnaphthalenes having low melting points.

If a solvent/diluent is used, the amount used conveniently ranges fromabout 5 mL to about 1 L per mole of ketone or aldehyde. Preferably, fromabout 200 mL to about 400 mL are used per mole of ketone or aldehyde.

The addition of water, generally in an amount up to a maximum of about5% by weight of total feed, is considered highly desirable in processesfor the preparation of bisphenol A, because water lowers the freezingpoint of phenol and addition of water permits the condensations to berun at lower temperatures than otherwise. Most preferably, the amount ofadded water is from about 1% by weight to about 5% by weight of totalfeed.

The reaction can advantageously be carried out by stirring the ketone oraldehyde and mercaptosulfonic acid into molten phenol in such a way thatthe temperature in the reaction vessel will not rise above about 150° C.

The molar ratio of phenolic reactant to ketone or aldehyde isadvantageously selected so that at least two moles of phenol willcondense with the ketone to produce a corresponding bisphenol or highercondensate. Therefore, molar ratios of 2:1 or higher will advantageouslybe selected. It is preferred to carry out the reactions using largerexcesses of phenolic reactant, up to as much as 50 moles of phenol permole of ketone or aldehyde. It will be understood that the excess phenolacts as a solvent or diluent, as well as a reactant.

Lower ratios of phenol to ketone/aldehyde are generally accompanied byan increase in the amount of by-products formed. In the preparation ofpolyphenols, it has been found that molar ratios from about 2:1 to about30:1 of phenol to aldehyde/ketone are preferred. More preferably, thereaction mixtures will contain from about 4:1 to about 25:1 molar ratiosof phenol to aldehyde/ketone. Most preferably, the molar ratio is fromabout 6:1 to about 25:1

Since the condensation reaction is exothermic, the reactants, instead ofbeing mixed together all at once, are optionally progressively mixedtogether at a speed depending upon the intensity of the cooling employedto maintain the temperature of the reaction medium within the optimumlimits. After the mixing of the reactants, they are preferably left incontact for some time in order to complete the condensation. Theduration of the introduction of the reactants during a batch processconveniently varies from 15 min to 1 h.

In batch processes, the reactants and the catalyst are preferablythoroughly stirred mechanically to assure better mixing, and hence animproved space-time yield.

When the process of this invention is conducted batchwise, the reactiontime is advantageously in the range of about 0.1 to about 20 hoursdepending on the reaction conditions including the amount of thecatalyst used, the reaction temperature, and specific reactants,solvents and products.

The process of this invention can also be run in continuous mode, morepreferably by use of a series of continuous stirred tank reactors, theuse of which approximates plug flow reaction conditions. It is preferredto carry out the process of this invention under continuous reactionconditions.

The pressure in the reaction zone is not critical, but preferably rangesfrom about 0.001 to about 10 bar (0.1 to 1000 kPa), and moreparticularly from about 0.5 to about 3 bar (50 to 300 kPa). In manycases, it will be preferred to carry out the reactions under ambientpressure, that is, about 1 bar (100 kPa).

During the reaction, one mole of water is evolved for each mole ofketone/aldehyde undergoing the condensation with phenol. It has beenfound that adding water to the reaction mixtures can be advantageous fordecreasing the melting point of phenol. The water evolved during thereactions need not be removed by distillation/entrainment with an inertsolvent in order to attain high reaction rates. In some cases, however,it will be preferred to entrain and remove water from the reactionmixture, in order to increase reaction rates.

It has been found that the soluble mercaptosulfonic acid catalysts canadvantageously be removed from the crude product by extraction withwater. The aqueous extracts can be concentrated and recoveredmercaptosulfonic acid catalyst can be optionally recycled to subsequentruns. When the phenolic starting material is phenol, a solution of themercaptosulfonic acid in phenol is conveniently recovered and isoptionally recycled without further purification.

The acid concentration can be reduced below about the limits ofdetection, and probably below about 1 ppm by weight of acid, by repeatedextractions with water. The facile removal of catalyst from the reactionmixtures is a significant advantage over the prior art, using mixturesof condensing agents. It is within the practice of this invention toremove the mercaptosulfonic acid by continuous countercurrentextraction.

The time for phase separation during extraction of the acid catalyst isof the order of 10-15 min under batch conditions, without a drag layer.Stirring speed during the extraction in a mixer/settler is adjusted soas to avoid emulsion formation.

The soluble mercaptosulfonic acid catalysts can also be removed fromreaction mixtures by extraction with a solution of an alkali metalhydroxide, carbonate or bicarbonate.

In addition, the soluble mercaptosulfonic acid catalysts can be removedfrom reaction mixtures by passing the reaction mixture through a columnof anion-exchange resin or amine resin, such as Dowex™ WGR.

A water purge from the process will contain phenol plus catalyst. Thispurge is advantageously treated to remove phenol by extraction withmethyl isobutyl ketone before being sent to a bio-pond for disposal.

For isolation of BHPF from reaction mixtures, made using a solublecatalyst, a phenol/water mixture is preferably distilled from thewater-washed mixture until the weight ratio of phenol:BHPF is belowabout 1.5:1. Most preferably, phenol is removed until the phenol:BHPFweight ratio is from about 1.5:1 to about 0.5:1. It has been foundparticularly advantageous to dissolve the resulting material in hotmethylene chloride and cool the resulting solution to obtain crystallineBHPF.

Very highly purified BHPF accordingly can be obtained by a processwherein a resulting crude product is washed with water to remove(HS)_(a) --θ--(SO₃ H)_(b) ; the resulting acid-free mixture is distilledto remove phenol and water until thephenol:9,9-bis-(4-hydroxyphenyl)fluorene weight ratio is less than about1.5; the resulting mixture is taken up in hot methylene chloride and theresulting solution is cooled to produce crystalline9,9-bis-(4-hydroxyphenyl)fluorene. BHPF purified in this way can be usedto make ultrahigh quality polycarbonate resins.

Excess phenol can also be removed by boiling the reaction mixturerepeatedly with water, optionally with the use of a water-miscibleorganic solvent such as methanol. The aqueous solution is separated eachtime and the product, then practically pure, is dried. Another effectivemethod of removing excess phenol is by steam distillation.

The reaction product solution is optionally then concentrated byevaporation and repeatedly extracted with boiling water for the removalof excess phenol. The product so obtained is optionally thenrecrystallized for further purification.

BHPF can be isolated from the reaction mixtures in several additionalways. The method selected will depend on the degree of purificationdesired as well as the composition of the reaction mixture, the desiredproduction rate, etc.

When extensive purification is undesirable or inappropriate, themixture, after being treated to remove catalyst, can be treated with avolume of hot water sufficient to dilute the mixture and bring aboutprecipitation of BHPF. Alternatively, the reaction mixture can be addedto hot water and the phenol removed in the form of a water/phenolazeotrope until the phenol content is lowered sufficiently to permitprecipitation of BHPF from the mixture. The BHPF solids can be collectedand dried before use or can be used in the form of a slurry.

When more extensive purification of BHPF is desired, the solids can bepurified by precipitation from a solvent, e.g. diphenylmethane ormethylene chloride.

Another method for isolating BHPF comprises adding to the reactionmixture, at the end of the reaction, a solvent, boiling at a highertemperature than phenol, and removing phenol from thephenol/BHPF/solvent mixture until BHPF crystallizes or precipitates fromthe mixture. This method can be carried out by adding diphenylmethane ortriisopropylbenzene to a reaction mixture, from which catalyst has beenextracted or removed, prior to distilling the mixture. Alternatively,the solvents can be added to the initial reaction mixture so that thereactions are run in the presence of the solvent. The reaction mixtureis worked up by extracting to remove catalyst and by then distilling toremove solvent and phenol, until BHPF crystallization occurs.

BHPF can also be isolated by adding to a reaction mixture a solvent,which boils at a higher temperature than phenol and dissolves sufficientBHPF, in the absence of phenol, that removing phenol from thephenol/BHPF/solvent mixture provides a homogeneous solution, cooling ofwhich causes crystallization of BHPF. Solvents meeting theserequirements include diphenylmethane, diphenyl ether, dodecane,naphthalene, Isopar™ (hydrocarbon mixture commercially available fromExxon Corporation) and triisopropylbenzene.

Further purification can also be accomplished, after removing catalystfrom the reaction mixture, by distilling to remove phenol to a level atwhich BHPF crystallizes from the phenol/BHPF mixture. The BHPF solidsobtained can be isolated by conventional means and then further treated,e.g., by washing with water to remove phenol.

An alternative method for obtaining high purity BHPF comprises removingcatalyst from the reaction mixture, distilling phenol from the reactionmixture to a phenol/BHPF level such that dilution of the distillationresidue with a solvent induces crystallization of the BHPF from thephenol/BHPF/solvent mixture. For example, phenol can be removed bydistillation until the distillation residue contains about 50% by weightof phenol and about 50% by weight of BHPF. Methylene chloride,triisopropylbenzene or toluene can be added to the residue and theresulting solution can be cooled to bring about crystallization ofhighly purified BHPF.

Another procedure for isolating pure BHPF solid from the reactioncomprises removing the mercaptosulfonic acid catalyst, distilling phenolfrom the resulting mixture, to produce a still residue, to whichaddition of a solvent induces crystallization of BHPF. For example, astill residue containing 80% by weight of phenol and 20% by weight ofBHPF can be diluted with a solvent, e.g. dichloromethane or toluene, toinduce crystallization of BHPF.

In addition, BHPF can be isolated from a reaction mixture, by removingthe mercaptosulfonic acid catalyst, adding to the resulting reactionmixture a solvent, which forms an azeotrope with phenol and in whichBHPF is soluble in the absence of phenol, and removing phenol from themixture by azeotropic distillation. Cyclohexanol is exemplary of asolvent, which will form an azeotrope with phenol and from which BHPFwill precipitate upon cooling the still residue from the azeotropicdistillation.

Similarly, phenol can be removed from the reaction mixtures by additionof a solvent, which forms an azeotrope with phenol. After removingphenol by azeotropic distillation, the still residue is cooled and BHPFcrystallizes out from the cooled mixture.

In any of the purification processes which result in a crystallineproduct, the catalyst is optionally not removed before crystallizationof product but rather either tolerated in the product or removed fromthe crystals, for instance by washing or other means within the skill inthe art, after crystallization.

In some cases, the condensation of phenol with ketones or aldehydes canbe run in a solvent, e.g., methylene chloride, from which the productwill precipitate during the course of the reaction, as is described inmore detail for the preparation of bisphenol A.

A representative solvent used for crystallization of BHPF, methylenechloride, can be recovered from the mother liquors by batch distillationand recycled back to the process. The still bottoms contain BHPF andmethylene chloride and can be cooled to recover additional BHPF. BHPFcrystals thus formed are conveniently recovered using a basketcentrifuge or pressure filter and can be recycled back to a maincrystallizer. Crude mother liquor can also be recycled back to thephenol evaporation section.

When methylene chloride is used as solvent for crystallizing BHPF, acommon vent header for collecting all vents from storage tanks andsafety relief systems is recommended. The vent header systemadvantageously includes a flow measurement device in the inlet to acarbon adsorption unit and a VOC analyzer for the exit gas. The exit gasshould contain less than 100 ppm of methylene chloride. A completeeffluent treating system will advantageously include means for removingorganics from process waters and means for removal of particulates fromvent gas, e.g a water venturi to scrub particulates from the ventheader.

A further advantage of the catalysts used in the practice of thisinvention is that the catalysts can be used to isomerize the crudeproduct mixture, which typically contains(4-hydroxyphenyl)(2-hydroxyphenyl) compounds, the majorbis-(4-hydroxyphenyl) compounds, and condensates, to produce more of thebis-(4-hydroxyphenyl) compounds.

The mercaptosulfonic acid catalysts of this invention are considerablyless corrosive to stainless steel than the mixed catalysts usedheretofore. Corrosion rates for stainless steel, below about 0.00254cm/year, have been measured. The reaction mixtures are believed to besubstantially free of halide ions, wherein "substantially free" meansless than about 5000 ppm of chloride ions.

The process of this invention is advantageously carried out underconditions such that the concentration of chloride is below about 5000ppm, preferably below about 1000 ppm, most preferably below about 100ppm.

It is believed that the low corrosion rate is related to the absence ofmineral acids, such as hydrochloric acid or sulfuric acid, from thereaction mixtures. The occurrence of corrosion in reactions usingmineral acids has been noted by Knebel et al. '594 and Faler '995,supra.

The insoluble catalysts of this invention can be filtered from thereaction mixtures, washed with a mixture of ketone/aldehyde and phenol,and recycled to subsequent runs. Alternatively, the insoluble catalystsare used in fixed beds and the condensations of phenols withaldehyde/ketone is done in continuous upflow, crossflow or downflowfashion. When fixed bed catalytic reactors are used, thecatalytically-active resins remain in the resin beds and need not beremoved.

Further embodiments of this invention will be determined by thereactants used, the catalyst selected, the diluent, if any, and thereactor employed.

For example, when using a soluble catalyst for the condensation ofphenol with 9-fluorenone, without a diluent, other than excess phenol orin the presence of a diluent which does not cause precipitation ofproduct, it will generally be preferred to use a high ratio of phenol tofluorenone to maximize selectivity to the desired bisphenol product.

A particularly preferred process is one wherein the molar ratio ofphenol:fluorenone is from about 4:1 to about 25:1; the reactiontemperature is from about 25° C. to about 50° C.; the catalyst ismercaptopropanesulfonic acid or mercaptobutanesulfonic acid, used in anamount from about 5 to about 10 molar % with respect to fluorenone; theprocess is carried out under ambient pressure or under vacuum to removewater of reaction and increase the reaction rate; no cosolvent is used;the catalyst is removed from the product by extraction with water usinga wash column or by batch extraction; the water extracts thus obtainedare concentrated and recycled to the process; the product is isolated byremoving excess phenol to a weight ratio from about 1.5:1 to about 0.5:1of phenol:BHPF and the product is precipitated with dichloromethane.

When an insoluble catalyst is used, a particularly preferred process isone wherein the molar ratio of phenol:fluorenone is from about 4:1 toabout 25:1; the condensation is carried out at a temperature from about40° C. to about 60° C.; no cosolvent is used; the catalyst is PMBSA; thecondensation is carried out in a continuous plug flow reactor; thereaction is carried out at ambient pressure or under reduced pressure toremove water of reaction and increase the reaction rate; the product isisolated by removing excess phenol to a weight ration from about 1.5:1to about 0.5:1 of phenol:BHPF and the product is precipitated withdichloromethane.

The process for making BHPF can also be carried out at molar ratios ofphenol:fluorenone from about 7:1 to about 5:1 in the presence of about0.05 to about 0.15 equivalent of MPSA or MBSA per mole of fluorenone,wherein methylene chloride is added to the reaction mixture afterconversion of at least 20% of fluorenone has occurred; heating theresulting mixture under reduced pressure to remove an azeotrope ofmethylene chloride and water; and cooling the mixture at the end of thecondensation reaction to cause precipitation of BHPF.

The condensation of phenol with fluorenone can further be carried outusing a feed containing from about 5:1 to about 3:1 molar ratio ofphenol:fluorenone and about from about 0.05 to about 0.15 equivalent ofMPSA or MBSA per mole of fluorenone, diluted with from about 10% byweight to about 30% by weight of methylene chloride. Crystalline BHPFcan be collected from the cooled reaction mixture.

In addition, BHPF can be prepared from a reaction mixture, containingfrom about 18:1 to about 12:1 molar ratios of phenol:fluorenone andabout 0.025-0.075 equivalent of MPSA or MBSA per mole of fluorenone at atemperature from about 50° C. to about 80° C., wherein the mixture atthe end of the reaction is diluted with 10-20 volumes of water toextract mercaptosulfonic acid catalyst, the thus-washed mixture isdistilled to a phenol:BHPF weight ratio from about 1.5:1 to about 1:1and cooled to bring about crystallization of BHPF. The crystalline BHPFis removed by filtration and washed with methylene chloride and thenwith water.

A process in which the product is precipitated in the reaction mixtureis preferred for the preparation of bisphenol A, more particularly aprocess wherein the phenol:acetone feed contains from about 6:1 to about15:1 molar ratios of phenol:acetone; the condensation is carried out ata temperature from about 25° C. to about 35° C.; the reaction mixturecontains up to about 5% by weight of water to lower the freezing pointof phenol; the catalyst is 3-mercaptopropanesulfonic or4-mercaptobutanesulfonic acid in an amount from about 0.05 to about 0.50equivalent per mole of acetone in the acetone:phenol feed; the reactionis carried out under ambient pressure; and the crystalline bisphenol Aproduced by the process is removed by filtration or centrifugation.

Further processing can include washing the bisphenol A with water topartially remove soluble catalyst, and removing additional solublecatalyst by treatment with an anion exchange resin. It is believed thata preferred reactor configuration for this process is a series ofcontinuous stirred tank reactors, so as to approximate plug flowreaction conditions.

Other process variations, include, but are not limited to:

(a) preparation of bisphenol A in neat phenol, using a soluble catalyst,with precipitation of bisphenol A in the reaction mixture and

(b) preparation of bisphenol A in phenol with a complex-formingcosolvent and soluble catalyst, with precipitation of bisphenol A in thereaction mixture.

More particularly, it is preferred to select a catalyst wherein at least99% of the bisphenol A that crystallizes during the reaction is4,4-bisphenol A. Such catalysts include soluble mercaptosulfonic acidsin which a and b are each independently integers from 1 to 4. Preferredconditions include reaction temperatures from about 0° C. to about 50°C., more preferably from about 20° C. to about 40° C.

Representative complex-forming solvents for bisphenol A include diethylether, acetone, ethanol, propanol, dioxane, acetic acid, acetonitrile,methylene chloride or carbon tetrachloride. The complex-forming solventscomplex preferentially with the 4,4-diphenolic isomer so that theresulting complex has solubility properties, differing from that of theuncomplexed 2,4-diphenolic compound and can be readily separatedtherefrom.

These processes can be run under varying pressure and temperatureconditions, as well as reactant, cosolvent and catalyst concentrations,as can be determined by routine experimentation.

In one aspect, a most preferred process of this invention is thatwherein the ketone is 9-fluorenone, the phenol is unsubstituted and theproduct is 9,9-bis-(4-hydroxyphenyl)fluorene; the molar ratio of phenolto fluorenone is from about 8:1 to about 25:1; the reaction mixturecontains from about 0.05 to about 0.20 equivalent of mercaptosulfonicacid per mole of fluorene; the mercaptosulfonic acid compound is3-mercaptopropanesulfonic acid or 4-mercaptobutanesulfonic acid and theprocess is carried out at a temperature from about 45° C. to about 60°C.

An equally preferred process is that wherein the ketone is acetone, thephenol is unsubstituted and the product is2,2-bis-(4-hydroxyphenyl)propane; the molar ratio of phenol to acetoneis from about 6:1 to about 15:1; the reaction mixture contains fromabout 0.10 to about 0.50 equivalent of mercaptosulfonic acid per mole ofacetone; the mercaptosulfonic acid compound is 3-mercaptopropanesulfonicacid or 4-mercaptobutanesulfonic acid and the process is carried out ata temperature from about 15° C. to about 60° C.

Without further elaboration, it is believed that one skilled in the artcan, using the preceding description, utilize the present invention tothe fullest extent. The following preferred specific embodiments are,therefore, to be construed as merely illustrative and not limitative ofthe remainder of the disclosure in any way whatsoever.

In the following examples, the temperatures are set forth uncorrected indegrees Celsius. Unless otherwise indicated, all parts and percentagesare by weight.

Reactors

Reactor design 1: A 500-mL reactor prepared from PFA Teflon® is fittedwith a thermocouple port, water condenser topped with nitrogen inlet,mechanical stirrer, drain port, and sampling port. Heating is providedwith an infrared heat lamp and the temperature is controlled with anelectronic thermometer/temperature controller.

Reactor design 2: A capped 4 dram glass vial with a magnetic stirrer.Heating is regulated by placing the vial in a temperature-controlledaluminum block heater.

Reactor design 3: A 100-mL jacketed glass reactor is fitted with athermometer port, magnetic stirrer, nitrogen inlet, and sampling port.Heating is provided and the temperature is controlled by circulatingglycol solution of the appropriate temperature through the jacketedflask using a Neslab Model RTE-220 circulating bath.

Reactor design 4: A 1.5 L, 2 L, or 3 L jacketed glass reactor fittedwith a thermometer/sampling port, nitrogen inlet, and mechanicalstirrer. Heating is provided and the temperature is controlled bycirculating glycol solution of the appropriate temperature through thejacketed flask using a Neslab Model RTE-220 circulating bath.

Analytical

Analytical method 1: A Varian HPLC system (Model 9010 solvent deliverysystem, Model 9095 Autosampler, Model 9065 Polychrom diode arraydetector) interfaced with a Varian Star workstation is used foranalysis. Area percent analysis is reported at 282 nm. Percentconversion is determined by an external standard method using calibratedconcentration curves for each major component. Analytical HPLC samplesare prepared by careful quantitative dilution of reaction samples(range: 400-500 times dilution). Column: Waters Nova-Pak C-18 (60Angstrom, 4 micron, 3.9×150 mm). Chromatography conditions: flow rate1.0 mL/min, solvent gradient (solvent A=water, solvent B=acetonitrile) 0min: 65% A/35% B, 9 min: 60% A/40% B, 18 min: 55% A/45% B, 24 min: 45%A/55% B, 48 min: 5% A/95% B, 52 min: method end (10 min equilibrationbefore and after runs).

Analytical method 2: A Hewlett-Packard HPLC system (Model 1084B solventdelivery system, Model 79850B LC terminal) is used for analysis. Areapercent analysis is reported at 254 nm. Percent conversion is determinedby an external standard method using calibrated concentration curves foreach major component. Analytical HPLC samples are prepared by carefulquantitative dilution of reaction samples (range: 400-500 timesdilution). Column: Waters Nova-Pak C-18 (60 Angstrom, 4 micron, 3.9×150mm). Chromatography conditions: flow rate 1.0 mL/min, solvent gradient(solvent A=water, solvent B=acetonitrile) 0 min: 65% A/35% B, 9 min: 60%A/40% B, 18 min: 55% A/45% B, 24 min: 45% A/55% B, 36 min: 25% A/75% B,38 min: 65% A/35% B, 38 min: method end. NOTE: This method gives asmaller response (approximately one-half the area) for the 2,4-BHPF andthe two:three adduct BHPF peaks relative to the 4,4-BHPF peak thaneither methods 1 or 3 using the diode array detector.

Analytical method 3: A Varian HPLC system (Model 9010 solvent deliverysystem, Model 9095 Autosampler, Model 9065 Polychrom diode arraydetector) interfaced with a Varian Star workstation is used foranalysis. Area percent analysis is reported at 282 nm. Percentconversion is determined by an internal standard method using a solutionof 0.0508 wt % acetophenone in 60/40 (wt./wt. %) methanol/water forpreparing the samples. Analytical HPLC samples are prepared by carefulquantitative dilution of reaction samples. Column: Waters Nova-Pak C-18(60 Angstrom, 4 micron, 3.9×150 mm). Chromatography conditions: flowrate 1.0 mL/min, solvent gradient (solvent A=water, solvent B=methanol)0 min: 55% A/45% B, 20 min: 15% A/85% B, 25 min: 10% A/90% B, 30 min:55% A/45% B, 35 min: method end (10 min equilibration before and afterruns).

Analytical method 4: The experimental setup of Method 1 is used. Thechromatography conditions are: flow rate 1 mL/min, solvent gradient(solvent A=water, solvent B=methanol) 0 min: 55% A/45% B, 20 min: 15%A/85% B, 25 min 10% A/90% B. Analysis--Internal Standard method using0.0508% acetophenone in 60% methanol/water. Average rel. std. deviationsranges from 1 to 2%, depending upon peak analyzed.

Analytical method 5: The reaction mixture is diluted with acetonitrileto a concentration of 0.01-0.1% by weight of components and the dilutedsample is analyzed by HPLC on a Waters NovaPak C18 column (10.16cm×0.635 cm inner diameter) connected to a Varian 9100 UV detector, setat 280 nm. The column temperature is 30° C., the pressure is 140 atm at0 min, the absorption full scale for the detector is 2.0, the integratorattenuation is 3 and the chart speed is 0.5 cm/min. The autosamplerinjects 20 microliters of sample onto the column every 36 min. ReservoirA contains megapure water and reservoir B HPLC grade acetonitrile. Thefollowing protocol is used:

    ______________________________________                                        Time Flow Rate % B                                                              (min)             (mL/min)                                                  ______________________________________                                        0               1.0    40                                                       8 1.0 40                                                                      20 1.0 60                                                                     26 1.0 99                                                                     30 1.0 40                                                                   ______________________________________                                    

The peak area generated by each component in the sample is used with itsknown response factor, and the dilution ratio, to calculate theconcentrations of each component in the sample solution.

Reagents

Fluorenone (Aldrich 98%), ˜0.5% fluorene and methylfluorenes

Acetone (Baker reagent, dried over molecular sieves)

Diphenylmethane (Penta International, 99+% distilled grade)

Phenol (Dow Chemical 99+%), ˜100 ppm H₂ O+100 ppm impurities

Sodium 3-mercaptopropanesulfonate: Source A: 90% purity (Aldrich)

Source B: 90% purity (Raschig Corp.)

3-Mercaptopropanesulfonic acid (MPSA):

Source A: Prepared from 90% Aldrich sodium

3-mercaptopropanesulfonate by reaction with HCl or treatment in anion-exchange column

Source B: Prepared from 90% Raschig Corp. sodium3-mercaptopropanesulfonate

Sodium 2-mercaptoethanesulfonate: 98% (Aldrich)

4-Mercaptobutanesulfonic acid (MBSA): prepared from 1,4-butanesultone(Aldrich) by reaction with NaSH, Ba(SH)₂ or an alkali metal thioacetatein accordance with R. Fischer, supra, A. Mustafa, supra, or Chem. Abs.,90:86742m (1979).

2-Benzyl-4-mercaptobutanesulfonic acid: prepared from 1,4-butanesultone(Aldrich) and benzyl bromide in accordance with M. B. Smith et al.,"Lithium Aluminum Hydride-Aluminum Hydride Reduction of Sultones," J.Org. Chem., vol. 46 (1981), pages 101-106 or T. Durst et al.,"Metallation of 5- and 6-membered ring sultones," Can. J. Chem., vol. 47(1969), pages 1230-1233.

2,3-Dimercaptopropanesulfonic acid: prepared from sodium2,3-dimercaptopropanesulfonate (Aldrich, 95%) by neutralization with HClor treatment with an acid ion-exchange resin, e.g. DOWEX™ MSC-1.

2,2-Bis(mercaptomethyl)-1,3-propanedisulfonic acid: prepared from2,2-bis(bromomethyl)-1,3-propanediol (Aldrich, 98%) as follows:

A mixture of 2,2-bis-(bromomethyl)-1,3-propanedisulfonic acid (200.0 g,0.764 mol, 1.00 equivalent) and sodium sulfite (211.7 g, 1.68 mol, 2.20equivalents) in 500 mL of deionized water is allowed to react underreflux (about 108° C.) for 28 h. At this time, additional sodium sulfite(105.9 g, 0.840 mol, 1.10 equivalent) is added and the mixture isallowed to react for 3 additional days under reflux. At this point, themixture consists of a clear solution and a considerable amount ofsolids.

The mixture is cooled to room temperature and saturated with gaseoushydrogen chloride. An exotherm to 43° C. is observed. The mixturebecomes homogenous and yellow in color during the early stages of HCladdition. As the mixture becomes saturated with HCl, a voluminous whiteprecipitate is formed. The solution is cooled to room temperature andfiltered to remove solid salts, which are primarily sodium chloride andsodium bromide. Water is removed from the filtrate to provide2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid (190.7 g) as a highlyviscous amber oil (glass).

Alternatively, the reaction mixture can be worked up by dilution withabout 200 mL of ethanol or methanol, after which the solid is removed byfiltration. Solvent is removed from the filtrate on a rotary evaporator,to produce a white solid containing mainly disodium2,2-bis-(hydroxymethyl)-1,3-propanedisulfonate. Concentratedhydrochloric acid can be added to the solid product to give the solubledisulfonic acid, plus insoluble sodium chloride and sodium bromide.

p-Xylene (400 mL) is added to the2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid and the resultingtwo-phase mixture is heated under reflux (about 135-150° C. pottemperature) to remove water, produced by the dehydration, in the formof an azeotrope in a Dean-Stark trap. After 8 hours' heating underreflux, the mixture is allowed to cool to room temperature and the upperxylene phase is decanted from the lower viscous product phase. Water(about 300 mL) is added to the cooled, lower phase containing2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid bis-sultone toproduce a large mass of white solid. The white solid (bis-sultone) isremoved by filtration, slurry washed extensively with water and withmethanol and dried in a vacuum oven To a solution of sodium bicarbonate(9.6 g, 114 mmol, 2.6 equivalents) in 30 mL of water is slowly addedthiolacetic acid (7.5 g, 96 mmol, 2.2 equivalents). The resultingsolution of sodium thiolacetate is added to a solution of2,2-bis-(hydroxymethyl)-1,3-propanedisulfonic acid bis-sultone (10 g,43.8 mmol, 1.00 equivalent) in 280 g of acetonitrile. After all thethiolacetate is added, the resulting mixture is allowed to standovernight at ambient temperature. Solvent is removed using a rotaryevaporator to give 19.6 g of ring-opened bis-(thioacetate) adduct as atan, flaky solid.

The thioacetate adduct (18.2 g) is hydrolyzed by stirring overnight atambient temperature in a nitrogen-saturated mixture of 10% sodiumhydroxide (20 g) and 100 g of water. The mixture is acidified to pH 3with 10% aqueous hydrochloric acid solution. Solvent is removed from theresulting mixture in a fume hood, using a rotary evaporator. The residueis dissolved in 50 mL of water and saturated with hydrogen chloride gas.The resulting solid salt is removed by filtration and the filtrate isconcentrated using a rotary evaporator to give2,2-bis-(mercaptomethyl)-1,3-propane-disulfonic acid as a viscousdark-colored oil.

Alternatively, the thioacetate adduct can be hydrolyzed by stirring withconcentrated hydrochloric acid, removing the solid salt product byfiltration and removing water from the filtrate using a rotaryevaporator.

Abreviations

nm=nanometers

uv=ultraviolet

rpm=revolutions per minute

mmol=millimoles

HPLC=high pressure liquid chromatography

BHPF=9,9-bis-(4-hydroxyphenyl)fluorene=4,4-isomer =BF

MPSA=3-mercaptopropanesulfonic acid

MBSA=4-mercaptobutanesulfonic acid

FN=Fn=9-fluorenone

2,4-isomer=9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene

DPM=diphenylmethane

BPA=2,2-bis-(4-hydroxyphenyl)propane=bisphenol A

n/d=not determined

EXAMPLE 1

Condensation of 9-Fluorenone with Phenol: (3-Mercapto-PropanesulfonicAcid)

9-Fluorenone (20.0 g, 0.111 mol. 1.0 equiv.) and molten phenol (156.7 g,1.66 mol. 15.0 equivalents) are added to a 500 mL PFA Teflon reactor(reactor design 1).

The reaction mixture is heated to 65° C. with stirring at 300-350 rpmunder a pad of nitrogen. 3-Mercaptopropane-sulfonic acid (0.864 g, 5.53mmol, 0.0498 equivalents) is added slowly over approximately 1 minute tothe reaction mixture at 65° C. The mixture turns dark yellow-orange uponadding the catalyst and gradually fades to a lighter yellow color as thereaction progresses. A slight exotherm to 66° C. is observed. Theexotherm persists for 10 minutes before the mixture cools to thereaction temperature of 65° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC (Analyticalmethod 1).

The 9-fluorenone is found to be completely consumed within 120 minuteswith a product composition, determined by quantitative HPLC, of 98% of9,9-bis-(4-hydroxyphenyl)-fluorene. The product is further analyzed by acombination of HPLC and UV (282 nm) and contains:

    ______________________________________                                        % by area   product                                                           ______________________________________                                        96.9        9,9-bis-(4-hydroxyphenyl)fluorene (BHPF)                             2.4 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)-                                  fluorene (2,4-isomer)                                                         0.7 adduct containing two fluorene units and                                  three phenolic units (two:three adduct)                                    ______________________________________                                    

EXAMPLE 2

Generation of 3-Mercaptoalkanesulfonic Acids from Their Sodiun Salts inthe Reaction Mixture

A. The procedure of Example 1 is repeated except that the catalyst isprepared in situ from 90 percent sodium 3-mercaptopropanesulfonate(0.854 g, 4.79 mmol, 0.0431 equivalents) and 95-98 percent sulfuric acid(0.48 g, 4.9 mmol, 0.044 equivalents) and the reaction is conducted at85° C.

The 9-fluorenone is completely consumed between 60 and 120 minutes,giving a final isomer distribution, determined as in Example 1, of:

    ______________________________________                                        % by area         product                                                     ______________________________________                                        95.3              4,4-isomer (BHPF)                                              3.6 2,4-isomer                                                                1.1 two-three adduct                                                       ______________________________________                                    

B. The procedure of Example 2A is repeated except that 98 percent sodium2-mercaptoethanesulfonate (0.779 g, 4.75 mmol, 0.0427 equivalents) and95-98 percent sulfuric acid (0.48 g, 4.9 mmol, 0.044 equivalents) areused as catalysts. The reaction is conducted at 85° C.

The 9-fluorenone is completely consumed within 60 minutes, giving aproduct isomer distribution, as described in Example 2A, of:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        91.7               4,4-isomer                                                    6.6 2,4-isomer                                                                1.7 two:three adduct                                                       ______________________________________                                    

These experiments demonstrate that 2-mercaptoethane-sulfonic acid,generated in the reaction mixture, is an effective condensing agent forthe process.

EXAMPLE 3

Condensation Using Sulfuric Acid and 3-Mercaptopropionic Acid(Comparative Example)

9-Fluorenone (20.0 g, 0.111 mol, 1.0 equiv.) and molten phenol (156.7 g,1.66 mol, 15.0 equiv.) are added to the reactor (reactor design 1). Thereaction mixture is heated to 65° C. with stirring a pad of nitrogen.3-Mercaptopropionic acid (0.588 g, 5.54 mmol, 0.0499 equiv.) is added tothe reaction mixture at 65° C., followed by the slow addition (over 1minute) of concentrated (95-98%) sulfuric acid (0.551 g, 5.62 mmol,0.0506 equiv.) to the reaction mixture at 65° C. The mixture turnspurplish-orange upon adding the sulfuric acid and gradually fades to ayellow-orange color within 5-10 minutes. A slight exotherm to 66-67° C.,is observed.

The exotherm persists for 15 minutes before the reaction mixture coolsto the reaction temperature of 65° C. The reaction is monitoredthroughout the reaction period by collecting samples and analyzing byHPLC. The 9-fluorenone is found to be completely consumed between 240and 420 minutes. HPLC analysis (analytical method 3) gives productdistribution:

    ______________________________________                                        % by area     product                                                         ______________________________________                                        93.0          9,9-bis-(4-hydroxyphenyl)fluorene                                  5.5 2,4-isomer                                                                1.5 two:three adduct                                                       ______________________________________                                    

This example shows that the prior art process is slower than the processof Examples 1 or 2 and that the resulting product contains less of the4,4-isomer, than produced by the process of Examples 1 or 2.

EXAMPLE 4

Effect of Added Water in Fluorenone Phenolations Using MPSA (Phenol asSolvent)

A. 9-Fluorenone (138.1 g, 0.770 mol, 1.00 equiv.) and molten phenol(1500 g, 15.9 mol, 20.8 equiv.) is added to the reactor (reactor design4, 2 L). The reaction mixture is heated to 45° C. with stirring under apad of nitrogen. 3-Mercaptopropanesulfonic acid (8.28 g, 53.0 mmol,0.0692 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 45° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. The9-fluorenone is found to be 22% consumed within 9 minutes, 52% consumedwithin 30 minutes, 76% consumed within 1 hour, 92% consumed within 1.75hours, and 100% consumed within 3.5 hours. HPLC analysis (analyticalmethod 3) gives the following relative area % analysis for the reactionproducts at 100% conversion:

    ______________________________________                                        % by area     product                                                         ______________________________________                                        96.9          9,9-bis(4-hydroxyphenyl)fluorene                                   2.4 2,4-isomer                                                                0.6 two:three adduct                                                       ______________________________________                                    

B. 9-Fluorenone (6.44 g, 0.0358 mol, 1.00 equiv.), molten phenol (70.0g, 0.744 mol, 20.8 equiv.), and deionized water (1.93 g, 0.107 mol, 3.00equiv.) is added to the reactor (reactor design 3). The reaction mixtureis heated to 45° C. with stirring under a pad of nitrogen.3-Mercaptopropanesulfonic acid (0.385 g, 2.47 mmol, 0.0690 equiv.) isadded slowly over approximately 1 minute to the reaction mixture at 45°C. The reaction is monitored throughout the reaction period bycollecting samples and analyzing by HPLC. The 9-fluorenone is found tobe 4% consumed within 9 minutes, 13% consumed within 1 hour, 29%consumed within 3.5 hours, and 94% consumed within 20.5 hours. HPLCanalysis (analytical method 3) gives the following relative area %analysis for the reaction products (fluorenone area not included) at 94%conversion:

    ______________________________________                                        % by area         product                                                     ______________________________________                                        96.5              BHPF (4,4-isomer)                                              2.9 2,4-isomer                                                                0.6 two:three adduct                                                       ______________________________________                                    

These experiments show that higher reaction rates and lower amounts ofundesirable by-products are obtained, in the absence of additionalwater.

EXAMPLE 5

Condensation of Fluorenone with Phenol Using Other Condensing Agents

A. 4-Mercaptobutanesulfonic Acid

9-Fluorenone (82.9 g, 0.460 mol, 1.00 equiv.) and molten phenol (900 g,9.56 mol, 20.8 equiv.) is added to the reactor (reactor design 4, 2 L).The reaction mixture is heated to 45 ° C. with stirring under a pad ofnitrogen. 4-Mercaptobutanesulfonic acid (5.41 g, 31.8 mmol, 0.0692equiv.) is added slowly over approximately 1 minute to the reactionmixture at 45° C. The reaction is monitored throughout the reactionperiod by collecting samples and analyzing by HPLC. The 9-fluorenone isfound to be 17% consumed within 5.5 minutes, 58% consumed within 30minutes, 83% consumed within 1 hour, 95% consumed within 1.75 hours, and100% consumed within 3.5 hours. HPLC analysis (analytical method 3)gives the following relative area % analysis for the reaction productsat 100% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        97.0               BHPF                                                          2.5 2,4-isomer                                                                0.5 two:three adduct                                                       ______________________________________                                    

B. 2.2-Bis-(mercaptomethyl)-1,3-propanedisulfonic Acid

To a 4 dram vial (reactor design 2) is added a mixture of fluorenone(0.40 g, 2.22 mmol, 1.00 equiv.) and phenol (2.10 g, 22.3 mmol, 10.0equiv.) The capped vial is placed into the heating control blockregulated at 63° C. and stirring is begun.2,2-Bis(mercaptomethyl)-1,3-propanedisulfonic acid (0.029 g, 0.098 mmol,0.044 equiv.) is added in one portion to the vial which is then tightlycapped. The reaction is monitored throughout the reaction period bycollecting samples and analyzing by HPLC. The 9-fluorenone is found tobe 25% consumed in 1.5 hours. HPLC analysis (analytical method 2) givesthe following relative area % analysis for the reaction products(fluorenone area not included) at 25% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        95.7               BHPF                                                          3.4 2,4-isomer                                                                0.9 two:three adduct                                                       ______________________________________                                    

C. 2,3-Dimercaptopropanesulfonic Acid

To a 4 dram vial (reactor design 2) is added a mixture of fluorenone(0.40 g, 2.22 mmol, 1.00 equiv.) and phenol (2.10 g, 22.3 mmol, 10.0equiv.) The capped vial is placed into the heating control blockregulated at 63° C. and stirring is begun. 2,3-Dimercaptopropanesulfonicacid (0.021 g, 0.011 mmol, 0.050 equiv.) is added in one portion to thevial which is then tightly capped. The reaction is monitored throughoutthe reaction period by collecting samples and analyzing by HPLC(analytical method 2). The 9-fluorenone is found to be 5% consumed in1.5 hours.

D. 3-Mercaptopropionic Acid and Methanesulfonic Acid (ComparativeExample)

To a 4 dram vial (reactor design 2) is added a mixture of fluorenone(0.460 g, 2.55 mmol, 1.00 equiv.) and phenol (5.00 g, 53.1 mmol, 20.8equiv.) The capped vial is placed into the heating control blockregulated at 55° C. and stirring is begun. 3-Mercaptopropionic acid(0.0217 g, 0.204 mmol, 0.080 equiv.) and methanesulfonic acid (0.0197 g,0.205 mmol, 0.080 equiv.) are added in one portion to the vial which isthen tightly capped. The reaction is monitored throughout the reactionperiod by collecting samples and analyzing by HPLC. The 9-fluorenone isfound to be 32% consumed within 30 minutes, 51% consumed within 1 hour,and 71% consumed within 2 hours. HPLC analysis (analytical method 3)gives the following relative area % analysis for the reaction products(fluorenone area not included) at 71% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        93.7               BHPF                                                          5.5 2,4-isomer                                                                0.8 two:three adduct                                                       ______________________________________                                    

E. 3-Mercaptopropionic Acid and Methylsulfamic Acid (ComparativeExample)

To a 4 dram vial (reactor design 2) is added a mixture of fluorenone(0.460 g, 2.55 mmol, 1.00 equiv.) and phenol (5.00 g, 53.1 mmol, 20.8equiv.) The capped vial is placed into the heating control blockregulated at 55° C. and stirring is begun. 3-Mercaptopropionic acid(0.0217 g, 0.204 mmol, 0.080 equiv.) and methylsulfamic acid (Aldrich98%) (0.0227 g, 0.204 mmol, 0.080 equiv.) are added in one portion tothe vial which is then tightly capped. The reaction is monitoredthroughout the reaction period by collecting samples and analyzing byHPLC. The 9-fluorenone is found to be 13% consumed within 1 hour, and21% consumed within 2 hours. HPLC analysis (analytical method 3) givesthe following relative area % analysis for the reaction products(fluorenone area not included) at 21% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        95.4               BHPF                                                          4.6 2,4-isomer                                                               n/d two:three adduct                                                        ______________________________________                                    

F. Substituion of Phosphonic Acids for Methanesulfonic Acid (ComparativeExamples)

The reaction conditions described in Example 5D are repeatedsubstituting each of the following acids (each at 8 mol %) formethanesulfonic acid in the reaction: sulfamic acid (Aldrich 98%),methylphosphonic acid (Aldrich 98%), and phenylphosphonic acid (Aldrich98%). In each case, very little conversion of the fluorenone is observedin comparison with the use of methanesulfonic acid.

These examples demonstrate that mixtures of a mercapto-compound and anacid are inferior to 3-mercaptopropane-sulfonic or4-mercaptobutanesulfonic acid for catalyzing the condensation of phenolwith fluorenone.

EXAMPLE 6

Effect of Water Concentration in Fluorenone Phenolations Using MPSA withDiphenylmethane as a Co-Solvent

A. 9-Fluorenone (3.65 g, 0.0200 mol. 1.00 equiv.), molten phenol (39.6g, 0.420 mol, 20.8 equiv.), deionized water (0.055 g, 3.06 mmol, 0.151equiv.) and diphenylmethane (32.83 g) is added to the reactor (reactordesign 2). The reaction mixture is heated to 53° C. with stirring undera pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.170 g, 1.10 mmol,0.0537 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 53° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. The9-fluorenone is found to be 49% consumed within 2 hours and 77% consumedwithin 4.5 hours. HPLC analysis (analytical method 3) gives thefollowing relative area % analysis for the reaction products (fluorenonearea not included) at 77% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        96.1               BHPF                                                          3.4 2,4-isomer                                                                0.5 two:three adduct                                                       ______________________________________                                    

B. 9-Fluorenone (3.65 g, 0.020 mol, 1.0 equiv.), molten phenol (39.6 g,0.420 mol, 20.8 equiv.), deionized water (0.362 g, 20.1 mmol, 0.994equiv.) and diphenylmethane (32.83 g) is added to the reactor (reactordesign 2). The reaction mixture is heated to 53° C. with stirring undera pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.158 g, 1.00 mmol,0.0500 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 53° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. The9-fluorenone is found to be 25% consumed within 2 hours, 45% consumedwithin 4.5 hours, and 57% consumed within 6 hours. HPLC analysis(analytical method 3) gives the following relative area % analysis forthe reaction products (fluorenone area not included) at 57% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        96.3               BHPF                                                          3.7 2,4-isomer                                                               n/d two:three adduct                                                        ______________________________________                                    

C. 9-Fluorenone (3.65 g, 0.0200 mol, 1.00 equiv.), molten phenol (39.6g, 0.420 mol, 20.8 equiv.), deionized water (1.09 g, 60.7 mmol, 3.00equiv.) and diphenylmethane (32.83 g) is added to the reactor (reactordesign 2). The reaction mixture is heated to 53° C. with stirring undera pad of nitrogen. 3-Mercaptopropanesulfonic acid (0.158 g, 1.00 mmol,0.0500 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 53° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. The9-fluorenone is found to be 11% consumed within 2 hours, 20% consumedwithin 4.5 hours, and 23% consumed within 6 hours. HPLC analysis(analytical method 3) gives the following relative area % analysis forthe reaction products (fluorenone area not included) at 23% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        95.9               BHPF                                                          4.1 2,4-isomer                                                               n/d two:three adduct                                                        ______________________________________                                    

These examples show that addition of large amounts of water to thereaction mixtures retards the condensation reaction.

EXAMPLE 7

Removal of Water Under Vacuum with and without Diphenylmethane as aCo-solvent

A. 9-Fluorenone (127.7 g, 0.709 mol, 1.00 equiv.) and molten phenol(996.1 g, 10.58 mol, 14.9 equiv.) is added to the reactor (reactordesign 4, 3 L). The reaction mixture is heated to 45° C. with stirringunder a pad of nitrogen. 3-Mercapto-propanesulfonic acid (5.53 g, 35.4mmol, 0.0500 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 45° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. The9-fluorenone is found to be 60% consumed within 1 hour, 88% consumedwithin 2 hours, and 95% consumed within 2.5 hours. HPLC analysis(analytical method 2) gives the following relative area % analysis forthe reaction products at 100% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.0               BHPF                                                          1.4 2,4-isomer                                                                0.7 two:three adduct                                                       ______________________________________                                    

B. 9-Fluorenone (127.7 g, 0.709 mol, 1.00 equiv.) and molten phenol(996.4 g, 10.59 mol, 14.9 equiv.) is added to the reactor (reactordesign 4, 3 L with a Dean-Stark water separation trap and vacuum inletattached in lieu of the nitrogen inlet). The reaction mixture is heatedto 45° C. with stirring. 3-Mercaptopropanesulfonic acid (5.53 g, 35.4mmol, 0.0500 equiv.) is added slowly over approximately 1 minute to thereaction mixture at 45° C. The reaction mixture is allowed to stir for15 minutes at atmospheric pressure, then vacuum is applied to thereactor. From this point on, the reaction is conducted under reducedpressure conditions (<5 mm Hg) with water/phenol distillate collected inthe Dean-Stark trap. The reaction is monitored throughout the reactionperiod by collecting samples and analyzing by HPLC. The 9-fluorenone isfound to be 68% consumed within 1 hour, 98% consumed within 2 hours, and100% consumed within 2.5 hours. HPLC analysis (analytical method 2)gives the following relative area % analysis for the reaction productsat 100% conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.1               BHPF                                                          1.3 2,4-isomer                                                                0.6 two:three adduct                                                       ______________________________________                                    

C. 9-Fluorenone (191.5 g, 1.063 mol, 1.00 equiv.), molten phenol (1500g, 15.9 mol, 15.0 equiv.) and diphenylmethane (156.7 g) are added to thereactor (reactor design 4, 3 L with a Dean-Stark water separation trapand vacuum inlet attached in lieu of the nitrogen inlet). The reactionmixture is heated to 45° C. with stirring. 3-Mercaptopropanesulfonicacid (8.27 g, 53.0 mmol, 0.0499 equiv.) is added slowly overapproximately 1 minute to the reaction mixture at 45° C. The reactionmixture is allowed to stir for 15 minutes at atmospheric pressure, thenvacuum is applied to the reactor. From this point on, the reaction isconducted under reduced pressure conditions (<5 mm Hg) with water/phenoldistillate collected in the Dean-Stark trap. The reaction is monitoredthroughout the reaction period by collecting samples and analyzing byHPLC. The 9-fluorenone is found to be 20% consumed within 15 minutes,80% consumed within 2 hours, 98% consumed within 3.5 hours, and 100%consumed within 6 hours. HPLC analysis (analytical method 2) gives thefollowing relative area % analysis for the reaction products at 100%conversion:

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.3               BHPF                                                          1.2 2,4-isomer                                                                0.5 two:three adduct                                                       ______________________________________                                    

These results show that removal of water from the reaction mixtures,containing diphenylmethane solvent, is unnecessary. These results showthat removing water from the reaction mixtures accelerates the rate ofthe phenolation reaction, but is not necessary for good reaction ratesand conversions.

EXAMPLE 8

Reaction of Phenol with Acetone to Produce Bisphenol A Using MPSACatalyst

A. To a 4 dram vial (reactor design 2) is added a mixture of acetone(0.11 g, 1.8 mmol, 1.0 equiv.) and phenol (2.40 g, 25.5 mmol, 14.0equiv.). The capped vial is placed into the heating control blockregulated at 62° C. and stirring is begun. 3-Mercaptopropanesulfonicacid (0.021 g, 0.13 mmol, 0.070 equiv.) is added in one portion to thevial which is then tightly capped. The reaction is monitored throughoutthe reaction period by collecting samples and analyzing by HPLC. Theacetone is found to be approximately 70% consumed within 2 hours. HPLCanalysis (analytical method 2) gives a relative area % ratio of 97.0:3.0for the desired reaction product 2,2-bis-(4-hydroxyphenyl)propane(4,4-bisphenol A) relative to the isomeric impurity2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)-propane (2,4-bisphenol A) at 70%conversion.

B. To a 4 dram vial (reactor design 2) is added a mixture of acetone(0.11 g, 1.8 mmol, 1.0 equiv.) and phenol (2.40 g, 25.5 mmol, 14.0equiv.). The capped vial is placed into the heating control blockregulated at 25° C. and stirring is begun. 3-Mercaptopropanesulfonicacid (0.074 g, 0.47 mmol, 0.25 equiv.) is added in one portion to thevial which is then tightly capped. The reaction is monitored throughoutthe reaction period by collecting samples and analyzing by HPLC. Theacetone is found to be approximately 70% consumed within 2 hours. Duringthe later stages of reaction, the reaction product begins to crystallizefrom the reaction mixture. HPLC analysis (analytical method 2) gives arelative area % ratio of 98.9:1.1 for the desired reaction product2,2-bis-(4-hydroxy-phenyl)propane (4,4-bisphenol A) relative to theisomeric impurity 2-(2-hydroxyphenyl)-2-(4-hydroxyphenyl)propane(2,4-bisphenol A) for the bulk reaction solution.

Separation of the crystalline product from the reaction mixture followedby rinsing of the crystals with water to remove surface impuritiesprovides 4,4-bisphenol A product containing less than 500 parts permillion of the 2,4-bisphenol A impurity.

C. (Comparative Example) To a 4 dram vial (reactor design 2) is added amixture of acetone (0.11 g, 1.8 mmol, 1.0 equiv.) and phenol (2.40 g,25.5 mmol, 14.0 equiv.). The capped vial is placed into the heatingcontrol block regulated at 62° C. and stirring is begun.3-Mercaptopropionic acid (0.014 g, 0.13 mmol, 0.070 equiv.) andmethanesulfonic acid (0.013 g, 0.13 mmol, 0.070 equiv.) are added in oneportion to the vial which is then tightly capped. The reaction ismonitored throughout the reaction period by collecting samples andanalyzing by HPLC. The acetone is found to be approximately 70% consumedwithin 2 hours. HPLC analysis (analytical method 2) gives a relativearea % ratio of 96.2:3.8 for the desired reaction product2,2-bis-(4-hydroxyphenyl)propane (4,4-bisphenol A) relative to theisomeric impurity 2-(2-hydroxyphenyl)-2-(4-hydroxy-phenyl)propane(2,4-bisphenol A) at 70% conversion.

These experiments show that MPSA gives a product, with a higher4,4-isomer ratio than prior art catalysts.

EXAMPLE 9

Preparation of the Polymer-Supported Mercaptosulfonic Acid Catalyst(PMBSA)

A. Preparation of Sultone Intermediate

1,4-Butanesultone (3.00 g, 22.0 mmol, 1.00 equivalent) is added to dryTHF (150 mL) under a nitrogen atmosphere. The solution is cooled to -78°C. using a dry ice/acetone bath. n-Butyllithium (1.6 molar in hexanes,13.8 mL, 1.00 equivalent) is added slowly dropwise to the -78° C.solution via an addition funnel over approximately 40 minutes withvigorous stirring. The homogeneous reaction mixture is allowed to stirfor an additional 10-15 minutes at -78° C. Poly(vinylbenzylchloride)(3.3 g, approximately 1.0 equivalent of chloromethyl groups, 60/40mixture of 3- and 4-isomers, Aldrich Chemical Co.) in dry THF (10 mL) isadded over approximately 2 minutes to the reaction mixture at -78° C.The reaction mixture is allowed to slowly warm to room temperature inthe cooling bath over approximately 3 hours. A white precipitate formsin the reaction mixture during the reaction period and remains as asolid as the mixture reaches room temperature. Water (100 mL) is addedto the reaction mixture and the white (insoluble) solid is removed byfiltration under vacuum. The solid is slurry-washed with water, thenwith small volumes of methanol and methylene chloride and dried in avacuum oven, providing 4.77 g of a white solid sultone-functionalpolymer.

B. Conversion of the Sultone-Functional Polymer to Polymer-SupportedMecaptosulfonic Acid (PMBSA)

The sultone-functional polymer from above (4.00 g, approximately 15.9mmol sultone) is added to THF (125 mL). Potassium thioacetate (2.20 g,19.0 mmol, 1.20 equivalent) is added as a solid to the slurry of thepolysultone in THF. One drop of 50% tetrabutylammonium chloride is addedto the rapidly stirred slurry. The temperature rises to 26° C. overseveral minutes, then slowly drops to 20° C. Two additional drops of 50%tetrabutylammonium chloride are added and the solution is warmed to 40°C. for 15 minutes. Water (100 mL) is slowly added over 1 hour to thereaction mixture at 40° C. Substantial solid remains in the mixture atall stages of the reaction. The water/THF reaction mixture is allowed toreact 15 hours at 40° C. The solvent is removed by rotary evaporationand the resultant solid is ground to a fine powder. THF (125 mL) isagain added to the solid, forming a slurry. Additional potassiumthioacetate (2.20 g, 19.0 mmol, 1.20 equivalent) is added, resulting inan exotherm to 26° C. Several drops of 50% tetrabutylammonium chlorideare added and the reaction mixture is heated to 40° C. for 15 hours. Thesolvent is removed by rotary evaporation. The tan solid is slurried in a2:1 (by volume) mixture of toluene/ethanol. Concentrated hydrochloricacid (50 mL) is added and the mixture is stirred at room temperatureovernight. Most of the HCl is removed by sparging the mixture withnitrogen, then the solvents are removed by rotoevaporation. The lighttan solid is slurry-washed extensively with 10% hydrochloric acid andwith water. Drying overnight in a vacuum oven (60° C./full vacuum)provides 4.18 g of the polymer-supported mercapto-sulfonic acid as alight tan solid.

C. Preparation of a Gel PMBSA Catalyst (PMBSA-MER)

A catalyst is prepared as above, starting with Merrifield resin(200-400, 2% crosslinked, gel), treated with butanesultone. The productis identified as PMBSA-MER.

D. Preparation of Catalyst from Bromomethylated Macroporous Polystyrene(PMBSA-XEBR)

A catalyst is prepared as above, starting with bromomethylatedAmberlite™ XE-305 macroporous resin (4% crosslinked, 20-50 mesh, about3.7 meq Br/g).

E. Preparation of Catalyst from Chlorometylated Macroporous Polystyrene(PMBSA-XECL)

A catalyst is prepared as above, starting with chloromethylatedAmberlite™ macroporous resin (4% crosslinked, 20-50 mesh, about 4.3 meqCl/g).

F. Preparation of Catalyst from Merrifield Resin and 1,3-propanesultone(PMPSA-MER)

Catalyst is prepared above, by treating Merrifield resin (2%crosslinked, 200-400 mesh, 4.3 meq Cl/g) with lithiated1,3-propanesultone, which can be prepared in accordance with T. Durst eta.,. "A new route to 5- and 6-membered ring sultones," Can. J. Chem.,vol. 48 (1970), pages 845-851.

EXAMPLE 10

Evaluation of a Mercaptosulfonic Acid Polymer (PMBSA) in the Reaction ofPhenol with Fluorenone

A. To a 4 dram vial equipped with a stirring bar (reactor design 2) isadded 4.33 grams of a 20.8:1 mole ratio mixture of phenol to fluorenoneand 0.26 g (6% by weight of the reactant solution) of themercaptosulfonic acid polymer (PMBSA) prepared as in Example 9B. Thereaction mixture consists of a homogeneous liquid phase plus a separateheterogeneous polymer catalyst phase. The mixture is heated to 36° C.for 3 hours. To increase the rate of reaction the temperature isincreased to 50° C. for 18 hours. Monitoring of the reaction by HPLCshows some reaction at 36° C. and 100% conversion after 18 hours at 50°C. HPLC analysis (analytical method 2) gives the following relative area% analysis for the products after 18 hours of reaction (100%conversion):

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.86              BHPF                                                          0.98 2,4-isomer                                                               0.16 two:three adduct                                                      ______________________________________                                    

B. (Comparative Example) Dowex™ 50WX4 (a crosslinked sulfonatedpolystyrene resin, The Dow Chemical Company) promoted with2,2-dimethylthiazolidine (25% of the resin sulfonic acid equivalents) iswashed on a glass filter frit with phenol at 55° C. to remove water. Theresin is then washed with a mixture consisting of a 20.8: 1 mole ratiomixture of phenol to fluorenone at 55° C. to displace the originalphenol wash. To a 4 dram vial equipped with a stirring bar (reactordesign 2) is added 2.13 grams of a 20.8:1 mole ratio mixture of phenolto fluorenone and 0.74 g (35% by weight of the reactant solution) of thepromoted Dowex™ 50WX4 catalyst activated as described above. The weightof catalyst used is determined after the reaction by recovery of theresin from the reaction mixture by filtration, washing the resin withtoluene and hexane, and drying to a constant weight in a vacuum oven at50° C. for 6 hours.

The reaction mixture consists of a homogeneous liquid phase plus aseparate heterogeneous polymer catalyst phase. The mixture is heated to50° C. for 18 hours. Monitoring of the reaction by HPLC showsapproximately 17% conversion after 4 hours and 73% conversion after 18hours at 50° C. HPLC analysis (analytical method 2) gives the followingrelative area % analysis for the products after 18 hours of reaction(73% conversion):

    ______________________________________                                        % by area          product                                                    ______________________________________                                        91.32              BHPF                                                          6.78 2,4-isomer                                                               1.90 two:three adduct                                                      ______________________________________                                    

C. (Comparative Example) To a 4 dram vial equipped with a stirring bar(reactor design 2) is added 2.16 grams of a 20.8:1 mole ratio mixture ofphenol to fluorenone and 0.34 g (16% by weight of the reactant solution)of dry Amberlyst™ 15 (a crosslinked sulfonated polystyrene resinavailable from Rohm and Haas Company). The reaction mixture consists ofa homogeneous liquid phase plus a separate heterogeneous polymercatalyst phase. The mixture is heated to 50° C. for 18 hours. Monitoringof the reaction by HPLC shows approximately 24% conversion after 4 hoursand 64% conversion after 18 hours at 50° C. HPLC analysis (analyticalmethod 2) gives the following relative area % analysis for the productsafter 18 hours of reaction (64% conversion):

    ______________________________________                                        % by area          product                                                    ______________________________________                                        95.82              BHPF                                                          3.93 2,4-isomer                                                               0.25 two:three adduct                                                      ______________________________________                                    

These experiments show that use of the catalysts disclosed herein giveshigher conversions of fluorenone and higher 4,4/2,4-isomer ratios thanthe prior art catalysts.

EXAMPLE 11

Recovery and Recycling of Solid Catalyst (PMBSA)

A. Catalyst Recovery

The reaction mixture from Example 10A is cooled to 40° C. and themixture is centrifuged. The upper liquid layer is decanted andadditional warm (40-45° C.) 20.8:1 mole ratio phenol/fluorenone solution(approximately 3-4 times the catalyst volume) is added. The mixture isstirred, centrifuged, and the warm liquid layer is decanted. This washprocedure is repeated for a total of three washes, then the requiredamount of phenol/fluorenone reactant mixture is added and the reactionis begun.

B. First Recycle

To the 4 dram vial containing the mercaptosulfonic acid polymerrecovered (as described above) from Example 11A is added 4.33 grams of a20.8:1 mole ratio mixture of phenol to fluorenone. The mixture is heatedto 50° C. for 4 hours. Monitoring of the reaction by HPLC showsapproximately 90% conversion after 4 hours at 50° C. HPLC analysis(analytical method 2) gives the following relative area % analysis forthe products after 4 hours of reaction (90% conversion):

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.77              BHPF                                                          1.09 2,4-isomer                                                               0.14 two:three adduct                                                      ______________________________________                                    

C. Second Recycle

To the 4 dram vial containing the mercaptosulfonic acid polymerrecovered (as described above) from the first recycle is added 4.00grams of a 20.8:1 mole ratio mixture of phenol to fluorenone. Themixture is heated to 50° C. for 18 hours. Monitoring of the reaction byHPLC shows approximately 83% conversion after 4 hours and 100%conversion after 18 hours at 50° C. HPLC analysis (analytical method 2)gives the following relative area % analysis for the products after 18hours of reaction (100% conversion):

    ______________________________________                                        % by area          product                                                    ______________________________________                                        98.79              BHPF                                                         1.10 2,4-isomer                                                               0.11 two:three adduct                                                       ______________________________________                                    

D. Third Recycle

To the 4 dram vial containing the mercaptosulfonic acid polymerrecovered (as described above) from the second recycle is added 2.00grams of a 20.8:1 mole ratio mixture of phenol to fluorenone. Themixture is heated to 40° C. for 18 hours. Monitoring of the reaction byHPLC shows approximately 90% conversion after 4.5 hours and 100%conversion after 18 hours at 40° C. HPLC analysis (analytical method 2)gives the following relative area % analysis for the products after 18hours of reaction (100% conversion):

    ______________________________________                                        % of area          product                                                    ______________________________________                                        99.08              BHPF                                                          0.92 2,4-isomer                                                              * two:three adduct                                                          ______________________________________                                         * not detectable                                                         

These experiments show that the catalyst can be recycled repeatedlywithout loss of activity.

EXAMPLE 12

Composite Experimental Determination of Parameters for the Condensationof Phenol with Fluorenone (3-MPSA Diphenyl-metane)

Experiments are run in stirred isothermal batch reactors (reactordesigns 2 or 3) to determine the effect of temperature, molar ratios ofreactants and amount of MPSA on reaction rates and product distribution.Results are shown in Table I.

Graphical analysis of the results in Table I shows that formation of2,4-BHPF is related to the reaction temperature. As the temperatureincreases, the 2,4/4,4 ratio increases. In contrast, the phenol/Fn moleratio has little effect on the 2,4/4,4 ratio. The yield of 2:3 adductincreases markedly as the ratio of phenol/Fn decreases from 15:1 to2.5:1 and the reaction temperatures is increased from 25° C. to 85° C.

Graphical analysis of results for runs at 18 mole % of MPSA, in terms ofinitial reaction rates (BHPF moles/L*hr) shows a marked rate increase ingoing from 25° C. to 85° C.

Increasing the concentration of MPSA catalyst also gives the expectedincrease in the reaction rate. The phenol:fluorenone ratio also affectsthe reaction rate. It is believed that higher ratios of phenol tofluorenone are beneficial for condensations, run in a solvent, such asdiphenylmethane.

                  TABLE I                                                         ______________________________________                                        PHENOL + Fn -----> BHPF                                                         Catalyst MPSA, 10% Fn in DPM                                                  Analytical Method 2 - UV Detector                                             Run     Temp.   Mole Mole %                                                                              2,4/4,4                                                                             2:3/4,4                                                                             Conv. Initial                          # (° C.) Ratio MPSA Area Area (%) Rates*                             ______________________________________                                         1    55      8.62   12.8  0.0261                                                                              0.0198                                                                              99    0.16                                2 25 2.46 7.9   14 0.0002                                                     3 85 2.46 7.9 0.0389 0.114 62 0.047                                           4 25 14.75 7.9   12 0.028                                                     5 85 14.75 7.9 0.0299 0.0098 99 0.53                                          6 25 2.46 17.7   5 0.001                                                      7 85 2.46 17.7 0.0334 0.102 67 0.59                                           8 25 14.75 17.7 0.0202 0.0074 99 0.041                                        9 85 14.75 17.7 0.0317 0.0106 99 0.88                                        10 25 8.62 12.8 0.0239 0.0179 99 0.0042                                       11 85 8.62 12.8 0.0354 0.0244 99 0.73                                         12 55 2.46 12.8 0.0252 0.0673 57 0.035                                        13 55 14.75 12.8 0.0237 0.0076 99 0.17                                        14 55 8.62 7.9 0.0264 0.0177 99 0.12                                          15 55 8.62 17.7 0.0291 0.0248 99 0.42                                         16 55 8.62 12.8 0.0285 0.0185 99 0.15                                         17 63 14.75 12.8 0.026 0.00911 99                                             18 63 14.75 12.8 0.0259 0.0088 99                                             19 63 14.75 12.8 0.026 0.0088 99                                              20 63 14.75 12.8 0.0266 0.0084 99 0.29                                         21** 63 14.75 12.8 0.0272 0.0096 99                                          22 63 14.75 12.8 0.0265 0.0098 98                                             23 63 14.75 12.8 0.0269 0.0092 98                                             24 55 14.75 17.7 0.0255 0.0084 98 0.36                                        25 55 2.46 17.7 -- -- 24 0.14                                                 26 63 9.9 5 0.0258 0.015 98 0.078                                             27 25 14.75 12.8 0.0178 0.0067 98 0.013                                     ______________________________________                                         Footnotes to Table I:                                                         BF = BHPF (4,4isomer)                                                         2:3 = two:three adduct                                                        *BHPF moles/L hr.                                                             **recycle                                                                

                                      TABLE II                                    __________________________________________________________________________    PHENOL + Fn -----> BHPF                                                         Catalyst MPSA, Various % Fn in Solvents                                       Analytical Method 2 - UV Detector                                              Temp          Mole                                                                             Mole %                                                                            2,4/4.4                                                                           2:3/4,4                                                                           Time                                                                              %                                           Run ° C. Solvent % Fn* Ratio MPSA Area Area hr Conv                  __________________________________________________________________________    1  65  DPM   21  10 18  0.029                                                                             0.017                                                                             2   98                                          2 55 DPM 55 15 6.5 0.012 0.008 4 100                                          3 33 DPM 38.4 30 11.5 0.013 0.005 2.5 95                                      4 45 DPM 55 20.8 14.6 0.016 0.006 2 100                                       5 45 DPM 55 15 5.0 0.013 0.005 6 100                                          1A 27 DPM/MC 29 21 4.6 0.010 0.005 19.5 100                                   2A 35 MBenzoate -55 21 8 0.015 0.004 6.5 86                                   3A 35 ClBenzene 13 21 25.6 0.018 0.005 3.25 99                                4A 35 2,4,6TMPh 14 21 14.6 0.014 0.002 3 38                                 __________________________________________________________________________     *In solvent                                                                   DPM = diphenylmethane                                                         DPM/MC = diphenylmethane + methylene chloride                                 MBenzoate = methyl benzoate                                                   ClBenzene = chlorobenzene                                                     2,4,6TMPh = 2,4,6Trimethylphenol                                         

The results in Table I show that the 2,4/4,4 ratio stays constant asconversion increases, whereas the 2:3/4,4 ratio increases.

The amount of MPSA catalyst is related to the amount of 2,4-isomericproduct formed. High 2,4/4,4 ratios at high concentrations of MPSA areprobably related to a shift toward an acid-catalyzed reaction to producerelatively higher amounts of 2,4-isomer.

EXAMPLE 13

Effects of Solvents on Product Distribution and Conversions

Experiments are run in stirred tank batch reactors to determine whetheruse of a solvent is advantageous. Results of these experiments are shownin Table II. The use of a solvent does not appear to be advantageous.Comparison of a run using 10% DPM with neat run, at the same MPSAconcentration, shows that reaction rates are higher for the neat run,although the DPM run uses 2.5 times more catalyst/Fn.

Higher 2,4/4,4 and 2:3-adduct ratios for the reactions in DPM is anotherdisadvantage. It is therefore preferred to run the condensations inexcess phenol as solvent.

EXAMPLE 14

Effects of Temperature, MPSA Concentration and Phenol/Fluorenone Ratioson Product Distributions (Excess Phenol as Solvent)

Reactions are done in isothermal stirred tank reactors as describedabove. Results are presented in Table III. These results demonstratethat increasing the amount of catalyst increases the 2,4/4,4 isomerratio. Increasing the reaction temperature or decreasing the phenol/Fnmole ratio leads to higher amounts of 2:3 adduct in the product mixture.

EXAMPLE 15

Recovery and Recycling of MPSA from the Reaction Mixtures

Runs of 100 mL to 1.5 L (reactor designs 3 and 4) are done to determinewhether MPSA can be extracted from the neat BHPF reaction solution withwater and recycled to subsequent runs. The effect of stirrer rpm on thetime required for breaking a resulting emulsion are also investigated.

Phenol is weighed and charged into the reaction vessel. Fluorenone isweighed and charged to the reaction vessel, followed by a weighedquantity of MPSA catalyst.

                                      TABLE III                                   __________________________________________________________________________    PHENOL + Fn -----> BHPF                                                         Catalyst MPSA, Neat Reactions - no solvent                                    Analytical Method 2 - UV Detector                                           Run Temp.                                                                              Mole                                                                              Mole %                                                                             Time                                                                              2,4/4,4                                                                           2:3/4,4%                                                                           %   MPSA                                         # (° C.) Ratio MPSA (hr.) Area Area Conv. **                         __________________________________________________________________________     1  65   10  5    2.2 0.017                                                                             0.011                                                                              99  0.0470                                        2 35 2 8 3 0.013 0.003 98 0.0382                                              3 55 21 8 1.5 0.016 0.004 100 0.0382                                          4 63 10 2 7.5 0.014 0.008 97 0.0187                                           5 63 15 13 1 0.017 0.005 -- 0.0846                                            6 28 10 5 20 0.011 0.008 92 0.0470                                            7 45 10 5 5 0.012 0.007 91 0.0470                                             8.sup.1 36 21 8 5 0.013 0.005 62                                              9 36 21 3.9 7.25 0.012 0.005 95 0.0191                                       10.sup.2 36 21 4 6.5 0.012 0.007 96 0.0202                                    11 35 21 159 1.83 0.028 0.011 100 0.6932                                      12* 45 15 5 2.5 0.013 0.006 99 0.0330                                         13 45 15 5 3.5 0.014 0.007 100 0.0330                                         14* 55 21 3 2 0.014 0.006 99 0.0146                                           15.sup.3 35 21 18 mpa 20 0.034 0.011 100 0.0580                                  5.2 msa                                                                  __________________________________________________________________________     * = vacuum used to remove water during reaction.                              **moles/L                                                                     .sup.1 Molecular sieves used to remove water while reaction is taking         place + more catalyst is added.                                               .sup.2 Fn added continuously over 43 min.                                     .sup.3 MSA (methanesulfonic acid) and MPA (mercaptopropionic acid) used       instead of MPSA                                                          

The concentrations of materials in the resulting mixtures are followedby HPLC (Analytical Method 4).

The following mixtures are used:

    ______________________________________                                        Neat Runs          DPM Runs                                                   Chem.   wt % theory    Chem.   wt % theory                                    ______________________________________                                        Phenol  82.35          Phenol  47                                               Fn 0.00 Fn 0.00                                                               MPSA 0.50 MPSA 0.21                                                           H.sub.2 O 0.84 H.sub.2 O 0.48                                                 BHPF 16.31 BHPF 9.3                                                             DPM 43                                                                    ______________________________________                                    

To the reactor is added 200 mL of the mixture and 200 mL of water. Theresulting mixture is stirred for 10 minutes. The phases are allowed toseparate and the separation time noted. A sample (10 mL) of the organicphase is removed for analysis by HPLC and I.C. (ion chromatography). Theaqueous phase is retained for analysis.

The extraction of the remaining organic layer is repeated, using anequal volume of water (190 mL). At the end of the extraction andseparation, 10 mL of the organic layer is retained.

The remaining 180 mL of organic layer is extracted with 180 mL of water.A 10-mL sample of the organic layer is retained, as before.

The aqueous extract is distilled under vacuum to give a solution ofphenol, MPSA and small amounts of BHPF. Acid titration and I.C. analysisindicates that all of the MPSA is recovered from the mixtures. Resultsof representative extractions are given in Table IV.

                                      TABLE IV                                    __________________________________________________________________________    Extraction Data for Neat 21:1 (Phenol/Fn) Run                                 __________________________________________________________________________    Extraction                                                                         1         2         3                                                    Phase                                                                              Org. Aq.  Org. Aq.  Org. Aq.                                             __________________________________________________________________________    (500 rpm Stirring Rate)                                                       g. used                                                                            217  200  251.4                                                                              190  216.2                                                                              180                                               g. end 262.2 154.9 226.9 214.5 196.4 199.8                                  % Component in Phase                                                          Phenol                                                                             62.8 6.71 57.6 6.63 59.2 6.39                                              Fn 0.00 0.0 0.00 0.0 0.00                                                     MPSA 0.08 0.55 0.030 0.12 0.0100 0.039                                        H.sub.2 O 23.7 92.7 28.0 93.3 25.1 93.6                                       BHPF 13.4 0.0098 14.4  15.8 0.0073                                          __________________________________________________________________________    Extraction                                                                         1         2         3                                                    Phase                                                                              Org. Aq.  Org. Aq.  Org. Aq.                                             __________________________________________________________________________    (150 rpm Stirring Rate)                                                       g. used                                                                            217  200  258  190  226.4                                                                              180                                               g. end 268.6 148.4 237.2 200.5 195.36 200.6                                 % Component in Phase                                                          Phenol                                                                             60.1 6.37 61.6 7.17 61.1 6.82                                              Fn 0.00 0.0 0.00 0.0 0.00                                                     MPSA 0.10 0.53 0.0270 0.10 -0.005 0.03                                        P-1 H.sub.2 O 27.1 93.1 24.2 92.7 23.5 93.2                                   P-2 BHPF 12.7 0.0088 14.3 -- 15.4 --                                        __________________________________________________________________________     ** 4th and 5th extractions: equal volumes of organic and water layers:        MPSA in organic 0.0030 (4th), 0.0005 (5th), in water 0.0143 (4th), 0.0025     (5th)                                                                    

EXAMPLE 16

Isomerization Study in the Presence of MPSA

Reactions are done in stirred batch isothermal reactors (reactor design2). To the reactor is charged a mixture of 83.2% by weight of phenol,0.09% by weight of fluorenone, 13.2% by weight of BHPF, containing 0.92%by weight of 2,4-isomer and 0.68% by weight of 2:3 adduct. Variousamounts of MPSA are charged to the reactor. The resulting mixtures arestirred and heated. The compositions in the reactor at various times aredetermined by analytical method 4.

Compositions of other reaction mixtures are given in Table V. Resultsare given in Table VI.

These results show that heating mixtures, in the presence of MPSA,brings about isomerization of the reaction mixtures toward higherconcentrations of 9,9-bis-(4-hydroxyphenyl)-fluorene. The concentrationof higher adducts also increases as a result of prolonged heating.

                  TABLE V                                                         ______________________________________                                        COMPOSITIONS FOR ISOMERIZATION STUDY                                                     Temp     mole/L                                                                              mole/L   g Rx g                                       Run ° C. MPSA Phenol Mix MPSA                                        ______________________________________                                        1      70       0.642   9.250    5.42 0.5710                                    2 55 0.340 9.705 5.42 0.2878                                                  4 55 0.920 8.835 5.42 0.8540                                                  6 55 0.642 9.250 5.42 0.5710                                                  8 70 0.340 9.705 5.42 0.2878                                                  9 70 0.920 8.835 5.42 0.8540                                                  15  55 0.180 9.940 5.42 0.1520                                              ______________________________________                                    

                                      TABLE VI                                    __________________________________________________________________________    ISOMERIZATION STUDIES                                                           % in Reaction Mixture                                                           Time                                                                             Phenol                                                                            Fn BHPF                                                                              2:4*                                                                             2:3*                                                                              2nd add.*                                                                          % Total.sup.+                                                                      Total*                                     __________________________________________________________________________    Run 1                                                                             0  75.27                                                                             0.08                                                                             11.94                                                                             1.74.                                                                            0.62                                                                              0.00 89.6 99.2                                         S#1 4 76.86 0.00 13.09 1.61 0.26 0.018 91.8 101.4                             S#2 22.5 74.64 0.00 14.05 1.01 0.17 0.15 90.0 99.5                            S#3 52 76.18 0.00 14.30 0.88 0.14 0.23 91.71 01.3                             Run 2 0 79.00 0.09 12.66 1.84 0.65 0.00 94.2 99.3                             S#1 4 81.9 0.0 13.1 1.9 0.5 0.00 97.4 102.5                                   S#2 21 76.71 0.00 13.21 1.56 0.29 0.0242 91.76 96.8                           S#3 29 80.41 0.00 14.07 1.53 0.23 0.0169 96.25 101.3                          S#4 94 80.96 0.00 14.18 0.89 0.14 0.07 92.17 101.2                            S#5 101 77.22 0.00 14.62 0.94 0.21 0.10 92.99 98.0                            Run 4 0 71.88 0.08 11.52 1.66 0.59 0.00 85.7 99.3                             S#1 2 67.53 0.06 12.25 1.68 0.40 0.00 81.92 95.5                              S#2 4.5 69.3 0.0 12.2 1.5 0.3 0.013 83.3 96.9                                 S#3 24.5 74.49 0.07 13.18 0.95 0.15 0.04 88.88 102.5                          S#4 88 67.54 0.00 13.95 0.70 0.11 0.22 82.29 95.9                             Run 6 0 76.02 0.08 12.06 1.75 0.62 0.00 90.5 100.1                            S#1 2 73.72 0.00 13.01 1.83 0.51 0.00 89.0 98.6                               S#2 4.5 75.4 0.0 13.2 1.8 0.4 0.0 90.8 100.3                                  S#3 24.5 78.39 0.00 13.36 1.17 0.18 0.02 93.13 102.7                          S#4 88 74.06 0.00 14.99 0.76 0.10 0.12 89.90 99.4                             Run 8 0 84.03 0.09 13.33 1.94 0.69 0.00 100.1 105.1                           S#1 7 78.92 0.00 14.00 1.69 0.29 0.00 94.90 99.0                              S#2 23 76.1 0.00 14.6 1.2 0.2 0.1 92.2 97.2                                   S#3 52 79.09 0.00 14.92 1.02 0.15 0.12 95.30 100.3                            Run 9 0 72.59 0.08 11.52 1.68 0.59 0.00 86.5 100.1                            S#1 3 68.42 0.00 12.90 1.31 0.20 0.03 82.87 96.5                              S#2 7 70.5 0.0 13.2 1.0 0.2 0.1 84.8 98.4                                     S#3 22.5 70.86 0.00 12.99 0.76 0.16 0.19 84.95 98.6                           Run 15 0 80.93 0.09 12.97 1.87 0.66 0.00 96.5 99.1                            S#1 2 83.36 0.00 13.83 2.01 0.66 0.00 99.8 102.6                            __________________________________________________________________________     *estimated                                                                    .sup.+ including catalyst                                                

EXAMPLE 17

Purification of 9,9-bis-(4-hydroxyphenyl)Fluorenone

A. Precipitation from Methylene Chloride

A synthetic reaction mixture (105.5 g: 63% by weight, 66.5 g of phenol;20% by weight, 21.1 g of 4,4-BHPF and 17% by weight, 18 g of water) isplaced in a 500-mL round-bottom three-neck flask equipped with a heatingmantle/Variac, thermometer, stirring bar and distillation arm. A"Therm-O-Watch" is used to control temperature of the liquid in theflask. A separate thermometer is placed in the distillation tower tomonitor temperature in the vapor phase.

The mixture is stirred and heated at ambient pressure up to atemperature of 160° C., during which time distillation of phenol andwater occurs. Analysis of the reaction mixture indicates the phenol:BHPFmass ratio is 1:1. The reaction mixture, while still hot, is slowlyadded to 176 g of BHPF-saturated methylene chloride and the resultingmixture is slowly swirled to produce a homogeneous solution, clear andyellow in color. The mixture is allowed to cool to room temperaturewhich causes crystallization to occur.

The rod-like crystals present in the magma are analyzed by microscopeprior to filtration. Approximately 80% of the crystals viewed are longerthan 100 microns and have a diameter between 20 and 50 microns.

The crystal magma is filtered on a medium porosity glass frit, using avacuum produced by water jet. The filter cake is displacement-washedwith 79 g of BHPF-saturated methylene chloride and then 72 g of hot (90°C.) water. After drying at 65° C. in air overnight, 12.9 g of whiteproduct is recovered. Isolated yield is 61% and HPLC purity is 99.8%.

B. Washing with Sodium Bicarbonate Solution

Synthetic reaction mixture (105.5 g as in Example 17A) is combined with100 mL of a 2% by weight aqueous solution of sodium bicarbonate. Themixture is agitated and then the organic and aqueous layers are allowedto separate in a separatory funnel. The organic layer is drawn off. Thisprocess is performed a total of 4 times. Washed reaction mixture (85.2g: 58%, 58 g of phenol; 17.4%, 17 g of 4,4-BHPF and 25%, 21 g of water)is placed in the apparatus, described in Example 17A.

The mixture is stirred and heated at a pressure of 80-100 mm Hg, up to atemperature of 160° C., during which time distillation of phenol andwater occurs. BHPF-saturated phenol (100 g) is then added to thereaction mixture and the temperature of the mixture is controlled at 65°C. Crystallization begins within 1 h. The slurry is stirred overnight,after which the rod-like crystals present in the magma are analyzed bymicroscope before filtration. Approximately 30% of the crystals viewedhave a length greater than 100 microns and a diameter between 10 and 30microns.

The crystal magma is filtered on a medium porosity glass frit using avacuum produced by water jet. The brown filter cake isdisplacement-washed with 200 mL of room-temperature water and then stirwashed with the same amount of water. The brown/beige crystals are thenwashed with BHPF-saturated methylene chloride and then with ethylenedichloride. After drying at 65° C. in air overnight, 7 g of brownproduct Are recovered. The isolated yield is 47% and HPLC purity is99.7%.

C. Distillation of Phenol, Crystallization from Toluene

Synthetic reaction mixture (149 g: 17.5% by weight, 24 g of 4,4-BHPF; 95g of phenol and 30 g of water) are charged to the reactor, described inExample 17A. The mixture is stirred and heated at a pressure of 80-100mm Hg up to a temperature of 160° C., during which time distillation ofphenol and water occurs until the phenol:BHPF mass ratio is reduced toapproximately 1:1. There is no increase in adduct concentration.

The resulting mixture is added while still hot to 121 g ofBHPF-saturated toluene. The resulting homogeneous solution is allowed tocool to room temperature, during which crystallization occurs. Theresulting rod-like crystals present in the magma are analyzed bymicroscope prior to filtration. Approximately 20% of the crystals viewedhave a length greater than 100 microns and a diameter between 10 and 50microns.

The crystal magma is filtered on a medium porosity glass frit using avacuum produced by water jet. The pink filter cake is treated similarlyto other examples. After drying at 65° C. in air overnight, 18.5 g ofpink product are recovered. Isolated yield is 77% and HPLC purity is98.1%.

D. Distillation of Phenol; Crystallization from Methylene Chloride

Phenol and fluorenone are combined in the presence of3-mercaptopropanesulfonic acid (MPSA) to produce a reaction mixturewhich, after washing to remove the acid catalyst, contains 20 wt % of4,4-BHPF, 64 wt % of phenol and 16 wt % water. The reaction mixture isdistilled under water jet vacuum (approx. 80 mm Hg) up to a temperatureof 160° C. to yield a residue, containing approximately 50 wt % ofphenol and 50 wt % of 4,4-BHPF, i.e., a 1:1 phenol: 4,4-BHPF mass ratio.

The 1:1 mixture is cooled to 120° C. and then poured into 176 g of roomtemperature methylene chloride, that had been previously saturated with4,4-BHPF. This results in a clear homogeneous solution at reflux, whichis allowed to cool to room temperature. The crystallized mixture isfiltered under vacuum at room temperature. The filter cake isdisplacement washed with 79 g of BHPF-saturated methylene chloride (nostirring of the filter cake during the wash) and then stir-washed with72 g of hot water (90° C.). The resulting white filter cake is dried inair at 60° C. to provide a yield of 61 wt % of the 4,4-BHPF originallydetected in the reaction mixture.

E. Removal of Phenol-water Azeotrope

Approximately 380 g of a reaction mixture similar to that of Example 17Dare slowly dripped into 4 L of water at a temperature of 84° C. at apressure of 300 mm Hg. This dilution in water is accompanied by theremoval of phenol in the form of a water/phenol azeotrope. Thewater-insoluble materials then precipitate from the liquid phase as awhite powder. Approximately 64 g of "crude" BHPF is obtained in thismanner. The "crude" BHPF contains all the impurities originallycontained in the reaction mixture. The product is filtered, washed withboiling water and dried in air at 60° C. to provide a recovery of 96 wt% of the 4,4-BHPF originally detected in the reaction mixture.

F. Crystallization from Triisopropylbenzene

A reaction mixture (55.8 g: 63.1% by weight, 35 g of phenol; 14% byweight of 4,4-BHPF and 23% by weight, 12.8 g of water) is charged to a250-mL round bottom flask, otherwise fitted out as in Example 17A.Triisopropylbenzene (TIPB, 106.6 g) is added to the mixture in theflask, as a result of which the mixture separates into two phases, ofwhich the yellow reaction mixture is the lower.

The mixture is stirred and heated under vacuum, produced by a water jet(ca. 80 mm). After removal of water at 50-88° C., the mixture appearshomogeneous. The mixture is stirred and allowed to cool. Solids appearwhen the temperature reaches about 70° C. The mixture is allowed to coolto room temperature and filtered on a glass frit under vacuum. The whitesolids on the frit are washed with TIPB. The filter cake is leftovernight under vacuum (water jet) while air is pulled through thefilter cake.

Analysis of the resulting mother liquor shows that little of the phenolin the feed is removed as a result of distillation. The filter cakecontains 4.2 g of white, nearly free-flowing product (54% recovery,98.8% purity by HPLC).

G. Distillation to Remove Phenol; Crystallization from MethyleneChloride

A reaction mixture (98.8 g: 61% by weight, 60.3 g of phenol; 19.4% byweight, 19.2 g of 4,4-BHPF and 19.6% by weight, 19.4 g of water) ischarged to an apparatus, described in Example 17F. A collection flask isattached to the distillation arm and connected to a vacuum source (waterjet). The temperature set point is adjusted to 100° C. and heating isbegun.

    ______________________________________                                        Temp. (° C.)                                                                    Observations/Actions                                                 ______________________________________                                        50-55    boiling and distillation occur                                         100 slight bubbling                                                            set point raised to 120° C.                                           105 distillation restarts                                                     115 insignificant distillation                                                 set point raised to 140° C.                                           120 vigorous boiling, little distillation,                                     vapor temperature rising                                                     121 vigorous boiling, distillation starting,                                   vapor temperature 115° C.                                             122 vapor temperature 118° C.                                           break vacuum and remove sample: 34 g of                                       distillate collected, mixture in pot has                                      phenol:BHPF mass ratio of ca. 2:1                                             reconnect vacuum source and recommence heating                               124 vapor temperature is 119° C., distillation                          starts                                                                       125 vapor temperature is 119° C.                                        break vacuum and sample mixture                                               13.9 g of distillate collected                                                set point 120° C. at atmospheric pressure                              reconnect vacuum and recommence heating                                       phenol:BHPF 1.6:1 mass ratio in pot                                          129 vapor temperature 121° C.                                           distillation starts                                                          131 vapor temperature 123° C.                                           stop operation, remove sample                                                 42.4 g remain in pot; mixture in pot has                                      phenol:BHPF ratio ca. 1.12:1; 6.7 g of                                        distillate collected                                                       ______________________________________                                    

The pot residue at 110° C. is added to 172 g of fresh drum-grademethylene chloride in a bottle. The addition is done slowly in order toavoid excessive flashing or boiling of the methylene chloride. Theresulting mixture more or less separates into two layers, of which theupper layer is richer in the phenol:BHPF component. The mixture isswirled and becomes homogeneous. The bottle is sealed and placed in apan of cold water (ca. 10° C.).

    ______________________________________                                        Time                                                                            (hr:min.) Observations/Actions                                              ______________________________________                                        0:08        homogeneous yellow solution                                         0:18 homogeneous yellow solution                                              0:56 yellow solution, possibly small crystals                                 1:18 same                                                                     2:00 same                                                                     2:24 crystallization ongoing, quite a few crystals                            17:48   solid yellow crystalline mass breaks up                                easily                                                                        filter under vacuum through glass frit to                                     obtain slightly yellow crystals; recover                                      158.8 g of yellow mother liquors                                           ______________________________________                                    

The crystallizer bottle is rinsed with 29.7 g of fresh methylenechloride (not all solids dissolve), the resulting mixture being used todisplacement wash the filter cake, which improves slightly in color.

The filter cake is slurry washed with 49.4 g of fresh methylene chlorideand the resulting slurry is filtered under vacuum. The color of thefilter cake is unchanged.

The filter cake is displacement washed with 33 g of cold water, withouta change in the color of the cake. The filter cake is slurry washed with40 g of boiling water, without a change in the color of the cake.

The cake is dried in air under vacuum for ca. 2 h, transferred to awatch glass and dried in an oven overnight at 65° C. The cake isslightly yellow.

The mass balance for the process is:

    ______________________________________                                        g of BHPF                                                                     ______________________________________                                        19.2          in initial mixture                                                8.1 in mother liquors at end of operation                                     9.1 isolated product                                                          1.7 in wash                                                                   0.3 unaccounted for                                                         ______________________________________                                    

H. Crystallization from Diphenylmethane

1. A mixture of 28 g of DPM, 17.5 g of phenol, 5.4 g of BHPF (98:2 4,4-to 2,4-isomers, by HPLC) and 12 mg of MPSA is washed with water. Theresulting layers are separated and the water layer is removed. Phenol isdistilled from the organic layer to give a mixture containing 21.8 g ofDPM, 3.8 g of phenol and 5.4 g of BHPF. The mixture to cooled to roomtemperature to give an off-white precipitate, which is filtered andwashed with DPM. The washed cake is dried in an oven at 60° C. to give6.1 g of material, containing 70% by weight of BHPF and 30% by weight ofphenol. The mixture is stripped at 140° C. under nitrogen at <80 mm Hgto give 4.2 g of white solid. The solid, by HPLC analysis (analyticalmethod 5), contains 99.6% by area of the 4,4-isomer and 0.04% by area of2,4-isomer.

2. A reaction mixture from 15:1 phenol:fluorenone, containing 34.5% byweight of phenol and 10.5% by weight of BHPF, is diluted with 55% byweight of DPM. Phenol (80% of that initially present, maximumtemperature 105° C., 4.5 mm Hg) is removed by distillation to give,after crystallization from DPM, white BHPF melting at 221-222° C. Therecovery of BHPF is 78%. The material contains area 99.6% of the4,4-isomer by HPLC.

I. Crystallization from Neat Phenol

Phenol is distilled from the reaction mixtures to produce mixtures,containing less than 50:50 phenol:BHPF by weight. The resultingmaterials can be washed with methylene chloride. The products areinconsistent in color and contain small crystals, usually of the orderof 10-70 microns.

J. Precipitation of BHPF by Addition to Water

Addition of reaction mixtures to boiling water or steam removes somephenol as a phenol-water azeotrope. The resulting product retains mostof the extraneous isomers and adducts and comprises very small crystals,of the order of 10-20 microns. The maximum purity is of the order of97-98%.

Analytical data (HPLC) are given in Table VII for samples, prepared inaccordance with the practice of the invention and forcommercially-available materials.

K. Removal and Recovery of Phenol from BHPF Reaction Mixture

Excess phenol is removed from a reaction mixture to a 1:1 ratio ofphenol:BHPF using a falling film evaporator. This is accomplished at120° C./120 mm Hg. At this temperature, BHPF solubility in phenol isabout 45%.

After removing phenol, the BHPF-phenol mixture is kept at about 90° C.and stirred prior to addition of methylene chloride or othercrystallizing solvent.

BHPF is crystallized at room temperature under a nitrogen pad. A batchcrystallizer is cooled to 5-10° C. for several hours during which BHPFcrystallizes. Solid BHPF is separated from the resulting slurry using abatch pressure filter or basket filter. Optionally, a pressure filtercan be used. Methylene chloride or other solvent can be recycled to theprocess.

BHPF crystals are dried under vacuum.

Comparative Materials

BHPF from Sloss (Birmingham, Ala.): The sample evaluated is a dry solid,from lot number 9307-03.

BHPF from Isonova (Austria): The sample evaluated is designated "Isonova10/93".

BHPF from Rutgers Nease (State College, Pennsylyania): The dry solid isfrom lot number 9306099.

BHPF from Isovolta (Neudorf, Austria): The sample, used as standard forthe comparative studies, was received in 1988 and is designated"Isovolta 1988."

Analysis of the results in Table VII shows that 4,4-BHPF, purified bydistillative removal of phenol:water azeotrope and extraction withmethylene chloride, produces high purity BHPF.

                  TABLE VII                                                       ______________________________________                                                                       2:3                                              Sample    BHPF  Total                                                         Source Lot No. 4,4-BHPF 2,4-BHPF Add. Other Impur.                          ______________________________________                                        Sloss 9307-03  100      ˜0                                                                             0     0    0                                     Isonova 10/93 100 0 0  0.00                                                   MeCl.sub.2 Ex. 17D 99.94  0.06  0.06                                          Water Ex. 17E 97.59 1.87 0.40 0.14 2.41                                       ppt'd                                                                         Isovolta 1988 100 0 0  0                                                      Rutgers 93060099 99.28 0.58 0.14  0.72                                        Nease                                                                         DPM Ex. 17H 99.6                                                            ______________________________________                                    

EXAMPLE 18

Corrosion Studies

A. Reaction Mixtures for BHPF Process

Corrosion tests are performed using a representative reaction mixturefor the condensation of phenol with fluorenone using various catalysts.The tests are done using metal specimens 3.81 cm in length, 1.59 cm inwidth, 0.32 cm thick, and having a 0.64 cm hole centered in one end. Thespecimens are isolated from each other and the mounting rack usingpolytetrafluoroethylene shoulder washers. The specimens are exposed toboth the liquid and vapor phases of each test cell. The contents of thecells are stirred continuously and are maintained at the selectedtemperature using YSI temperature controllers and GLASCOL™ heatingmantles. The tests are run under a nitrogen pad. The chloride content ofthe test mixtures is <500 ppm. The tests are run at 65° C. for 13 days(312 h). Compositions tested and results are presented in Table VIII.

Results in Table VIII demonstrate that the reaction mixtures used areconsiderably less corrosive than conventionally used reaction mixtures.

                  TABLE VIII                                                      ______________________________________                                        CORROSION TESTING FOR BHPF REACTION MIXTURES                                      Metal      Liquid     Vapor Remarks                                       ______________________________________                                        A. Reactor Mixture: 90.2% of Phenol,                                            8.3% of Fluorenone, 1.5% of MPSA (by weight)                                  Corrosion Rate (mpy)*                                                           316L ss**    nil***   <0.1  uniform corrosion                               904L ss nil 0.1 uniform corrosion                                             2205 ss nil <0.1 uniform corrosion                                          254 SMO ss nil        nil     uniform corrosion                               B. Water Extraction Mixture: 8.0% of Phenol, 91% of                             Water and 1.0% of MPSA (by weight)                                            Corrosion Rate (mpy)                                                            316L ss    0.1        0.1   uniform corrosion                               904L ss <0.1 <0.1 uniform corrosion                                           2205 ss <0.1 <0.1 uniform corrosion                                           254 SMO ss <0.1 <0.1 uniform corrosion                                      C. Recycle Concentrate: 29.87% of Phenol, 69.23% of                             Water and 0.9% of MPSA (by weight)                                            Corrosion Rate (mpy)                                                            316L ss    0.1        0.1   uniform corrosion                               904L ss <0.1 <0.1 uniform corrosion                                           Inconel 625 <0.1 <0.1 uniform corrosion                                       Hastelloy C-27 0.1 <0.1 uniform corrosion                                     Hastelloy G-30 <0.1 <0.1 uniform corrosion                                  ______________________________________                                         *mpy = mils per year; 1 mpy = 0.00254 cm/yr                                   **ss = stainless steel                                                        ***nil = <0.01 mpy                                                       

B. Reaction Mixtures for Bisphenol A Process

A mixture containing 94.35% by weight of phenol, 4.15% by weight ofacetone and 1.50% of MPSA is evaluated as in Example 18A.

The following results are obtained:

    ______________________________________                                        Corrosion Rate                                                                       Metal       Liquid  Vapor                                              ______________________________________                                        304L ss        pass    pass                                                     316L ss pass pass                                                             904L ss pass pass                                                             2205 ss pass pass                                                             825 Ni pass pass                                                            ______________________________________                                         pass = <0.00254 cm/year                                                  

The corrosion rates in both the liquid and vapor phases is <0.00254cm/year. The corrosion is uniform. The rate of corrosion is below thatfor conventional reaction mixtures for making bisphenol A.

EXAMPLE 19

A. Preparation of Bisphenol A Using PMBSA

Bisphenol A is prepared from 14:1 phenol:acetone (mole ratio) at 50° C.,containing the indicated amounts of solid catalyst. The productdistribution is determined by analytical method 2.

The PMBSA catalyst of Example 9B, at a level of 6% by weight, givesabout 75% conversion after 5 h. The product contains 99.0:1.0 of4,4:2,4-isomers (area %).

The PMBSA is recovered and reused in a second cycle. The conversionafter 4 h is about 60%. The product contains 99.1:0.9 of 4,4:2,4-isomers(area %).

DOWEX™ 50WX4 (35% by weight as dry mass), promoted with 25% by weight of2,2-dimethylthiazolidine, is used in a similar experiment. Theconversion after 4 h is 43% and the product contains 98.0:2.0 (as area%) of 4,4:2.4-isomers.

These experiments show that a polymer-supported catalyst of thisinvention gives higher conversions and a higher yield of 4,4-isomer thana representative prior art catalyst.

B. Reaction Using PMBSA in a Downflow Continuous Reactor

The reactor comprises a vertical tube. The bottom part of the tube isfilled with glass beads, on top of which is provided a bed of PMBSAcatalyst resin. The remainder of the tube is filled with glass beads.The tube is fitted with a pressure gauge, a pressure regulator, heatingmeans external to the catalyst bed and feed means at the bottom of thetubular reactor for introducing the phenol and fluorenone reactants. Thefeed is prepared in a container, provided with a nitrogen stream andheated externally by a fluid. A valve is intermediate the feedpreparation container and a pump for introducing the feed into thebottom of the reactor. A relief valve is placed between the pump and thereactor.

The feed is introduced into the reactor at a predetermined rate andpasses upwardly through the lower bed of glass beads, which functions asa preheater, through the catalyst bed and the upper bed of glass beads,whereupon the product is removed from the top part of the reactor foranalysis or further processing.

Experiments using 21:1 phenol:fluorenone and PMBSA catalyst gave thefollowing results as a function of flow rate and reaction temperature:

    ______________________________________                                                          49° C.                                                                          69° C.                                      ______________________________________                                        Conversion (%)      80         100                                              BHPF in phenol (%) 14  16                                                     Productivity (g BHPF/g cat/h)  0.57  0.44                                     Selectivity (% 4,4-BHPF) 98.sup.+  97.sup.+                                   Flow rate (g feed/g cat · h)  4.39  2.71                           ______________________________________                                    

These experiments show that lower reaction temperatures favorproductivity and selectivity toward 4,4-BHPF, accompanied by decreasedconversion.

C. Conversion of Acetone as a Function of Reaction Temperature

Phenol-acetone mixtures (6% by weight acetone) are converted tobisphenol A, using MPSA as catalyst in batch reactors. The followingresults are obtained (Table IX):

                  TABLE IX                                                        ______________________________________                                        Acetone Conversion                                                                Time                                                                        (min) 25° C.* 35° C.* 55° C.+ 65° C.                                                     75° C.+                       ______________________________________                                         0     0         0.10    0.22    0.25  0.26                                      20   0.40 0.48 0.49                                                           25 0.04 0.42                                                                  40   0.59 0.62 0.67                                                           48   0.65 0.69 0.77                                                           60 0.06 0.56 0.69 0.75                                                        72     0.82                                                                   90 0.09  0.79 0.85 0.89                                                      120 0.13 0.72 0.83 0.89 0.94                                                  180 0.20 0.80  0.95 0.96                                                      240 0.26   0.97                                                               300    0.98                                                                   360 0.32    0.99                                                            ______________________________________                                         *mixture contains 2.2% by weight of MPSA and 2-3% by weight of water          +mixture contains 1.3% by weight of MPSA and no added water              

D. Removal of MPSA catalyst Using Ion-Exchange Resin; Purification ofCrystalline Bisphenbol A

Condensation of phenol with acetone (4% by weight), containing about 2by weight of water, using 2.5% by weight of MPSA, is done at 35° C. inplug flow mode, with a 3-h residence time. Crystallization of bisphenolA occurs in the reactor. The crystals are isolated by filtration andresidual acetone in the mother liquors is recycled to the process at 50°C. THE mother liquors are dried at 50° C. (20 mm Hg) and the cycle isrepeated after addition of make-up feed. About 90% of the acetone isconverted to bisphenol A per pass.

Catalyst is removed from the product by first melting the crystals andwashing the resulting oil with water, and then extracting the organiclayer with water, which reduces the acid concentration below about 100ppm after three equilibrium stages. The remaining catalyst is removedusing an anion exchange bed (<50 ppm, the limit of detection).

Bisphenol A, isolated by a single crystallization step, is of higherpurity than products, generally obtained using two crystallizations.Bisphenol A isolated by a single crystallization, contains a maximum ofabout 1200 ppm of 2,4-bisphenol. The process of this invention thereforesimplifies the isolation of high purity of bisphenol A, uncontaminatedby oily higher condensates.

EXAMPLE 20

Solid Catalyst Prepared from Polystyrene by Alkylation with AllylBromide, Sulfonation and Thiolation

A. Polystyrene (Amberlite® XE 305) is alkylated with allyl bromide inthe presence of trifluoromethanesulfonic acid in 1,2-dichloropropane at50° C., generally in accordance with Tomoi et al., "A Novel One-potSynthesis of Spacer-modified Polymer Supports and Phase-transferCatalytic Activity of Phosphonium Salts Bound to the Polymer Supports,"Reactive Polymers, vol. 3 (1985), pages 341-349, to produce a materialhaving 2-bromo-1-methylethyl chains. This material is sulfonated,generally at the ortho-position with respect to the side chain, bytreatment with chlorosulfonic acid. The resulting sulfonyl chloride isconverted to a sodium salt by reaction with sodium bicarbonate. Thematerial is converted to a corresponding thiol by reaction with sodiumthioacetate and converted to a corresponding acid by acidic hydrolysis.Materials prepared correspond to 28 and 48% of alkylmercaptanfunctionality (XEMSA).

B. The thus-prepared polymers (XEMSA) are used at a level of 6% byweight for reaction between phenol and fluorenone (20.8:1 mole ratio) at50° C. Product composition is determined by analytical method 3.

The polymer containing 28% of alkylmercaptan functionality gives 75%conversion after 5 h. The product distribution is 96.8:3.2 of4,4:2,4-isomers (area %).

The product containing 48% of alkylmercaptan functionality gives 15%conversion after 2 h. The product distribution is 96.8:3.2 of4,4:2,4-isomers (area %).

EXAMPLE 21

In Situ Method for Preparing the Polymer-Supported Mercaptosulfonic AcidCatalyst (MBSA Class):

A. Sultone Alkylation

To a mixture of 1,4-butanesultone (30.0 g, 220.0 mmol, 1.00 equivalent)and poly(vinylbenzylchloride) (PVBC, 33.6 g, approximately 220 mmol,1.00 equivalent) of chloromethyl groups) is added via a cannula drytetrahydrofuran (600 mL) under a nitrogen atmosphere. The mixture isstirred at room temperature until a homogeneous solution is obtained.The solution is then cooled to -78° C. using a dry ice/acetone bath.n-Butyllithium (2.5 molar in hexanes, 88.1 mL, 1.00 equivalent) is addedslowly dropwise to the -78° C. solution of 1,4-butanesultone andpoly(vinylbenzylchloride) via an addition funnel over approximately 2.5h with vigorous stirring. A white solid begins to precipitate from thereaction mixture as the n-butyllithium addition is begun, withprecipitation continuing throughout the n-butyllithium addition period.By the end of the addition, a large amount of white solid has formedwithin the reaction medium.

The reaction mixture (slurry) is allowed to slowly warm to roomtemperature in the cooling bath (over approximately 3-4 h) and isallowed to stir at room temperature overnight. The white precipitatewhich has formed in the reaction mixture during the n-butyllithiumaddition period remains insoluble as the mixture reaches roomtemperature. The white (insoluble) solid is removed by vacuumfiltration. The polymer can be washed with water or water can be addedto the THF/polymer slurry prior to filtration. Addition of watersometimes results in increasing the time required for filtration. Thesolid is slurry-washed with THF, then with methanol and finally withmethylene chloride (causing some swelling). The solid is dried overnightin a vacuum oven to provide 53.4 g of a white solid sultone-functionalpolymer.

B. Thiolation

To the sultone-functional polymer from above (110.0 g from two combinedbatches, approximately 0.440 mol of sultone) is added nitrogen-saturatedTHF (500 mL). In a separate reactor, a solution of lithium thioacetateis prepared by the dropwise addition of thiolacetic acid (49.8 g, 0.650mol) to a slurry of lithium carbonate (24.2 g, 0.330 mol) in water (100mL, nitrogen saturated). The lithium thioacetate solution is addedslowly via cannula to the polymer/THF slurry at such a rate that thetemperature does not rise above about 35° C. The polymer swellssubstantially during the lithium thioacetate addition. After the lithiumthioacetate addition is complete, an additional 350 mL of water(nitrogen saturated) is added. The polymer swells to a volume ofapproximately 1 L. The mixture is heated to 50° C., and is allowed toreact overnight. The gel-like polymer is then filtered using a coarseglass-fritted funnel. The polymer is washed with water, then withmethanol, then with methylene chloride, and finally with additionalwater. The polymer slurry sometimes filters very slowly during thefiltration process. In this case, the washing steps requiredapproximately two days.

After the washing steps, concentrated hydrochloric acid (300 mL,approximately 37% by weight in water) is added to the polymer. Thepolymer shrinks in volume and the HCl solution is easily removed byfiltration. More concentrated HCl (300 mL) is added to the filteredsolid, and the mixture is allowed to stand at room temperature over 2days. The polymer is then washed extensively with dilute HCl solution,followed by extensive water washes. The polymer is then washed withmethanol and finally with dichloromethane. Drying overnight in a vacuumoven (60° C./full vacuum) provides the polymer-supportedmercaptosulfonic acid. The product is identified as PMBSA-SU.

C. Conversion of Crosslinked Polystyrene Resin to Mercaptosulfonic AcidPolymer

A commercially-available (Fluka Chimika) crosslinked chloromethylatedMerrifield resin (2% divinylbenzene, 200-400 mesh, approximately 4.3mmol Cl/g, 51.2 g, 1.0 equivalent) is reacted with 1,4-butanesultone(1.05 equivalents) and n-butyllithium (1.0 equivalent) according to theprocedure described above to provide a sultone-functional polymer (70.0g). Subsequent thiolation of the sultone polymer in a manner similar tothat described above provides the corresponding mercaptosulfonic acidpolymer (79.0 g dry mass). This material is identified as PMBSA-MER.

In this reaction sequence, the lithium thioacetate reagent is formed insitu by slowly adding solid lithium carbonate to a mixture of thesultone polymer and thiolacetic acid in a 3:2 volume ratio ofnitrogen-saturated THF/water.

EXAMPLE 22

Preparation of Polymer-Supported Mercaptosulfonic Acid Catalyst (XEMSAClass)

A. Alkylation of Polystyrene

To Amberlitelm XE-305 (75.0 g, approximately 0.720 mol of styrene repeatunits, 1.00 equivalent) is added 600 mL of 1,2-dichloropropane (PDC).The polymer is allowed to swell in the solvent overnight.5-Bromo-1-pentene (75.3 g, 0.702 equivalent) and PDC (125 mL) are addedto an addition funnel. The reactor contents (polymer slurry and5-bromo-1-pentene solution) are evacuated and back-filled with nitrogenseveral times. Trifluoromethanesulfonic acid (20.0 g, 0.133 mol, 0.19equivalent) is added to the polymer/PDC slurry. The slurry solutionturns a dark amber color. The polymer slurry is heated to 45-50° C., andslow, dropwise addition of the 5-bromo-1-pentene solution is begun. The5-bromo-1-pentene solution is added slowly over approximately 3 days tothe stirred polymer slurry at 50° C. After the 5-bromo-1-penteneaddition is complete, the reaction is allowed to stir an additional 1day at 50° C. The polymer slurry is very dark-colored throughout theaddition period.

The polymer slurry (very dark red-brown) is cooled to room temperatureand filtered. The beads are washed extensively with dichloromethane(still dark colored beads) and then are washed extensively with water toremove most of the color. The beads are then washed with the followingseries of solvents: methanol, acetone, dichloromethane, acetone, and,finally, methanol. After drying in a vacuum oven at 60° C. overnight,96.46 g of nearly white bromoalkylated polymer beads are obtained. Themass uptake corresponds to a degree of functionalization (DF) ofapproximately 0.20.

B. Sulfonation

To the dried bromoalkylated polymer beads prepared above (approximately0.720 mol of styrene repeat units) is added 650 mL of dichloromethaneunder a nitrogen atmosphere sphere. The polymer slurry is cooled to 0°C. using an ice/water bath. Chlorosulfonic acid (258.2 g, 2.22 mol, 3.08equivalents) is added slowly dropwise to the polymer slurry at 0° C.over 2 h 40 min. The polymer beads turn copper-colored during thechlorosulfonic acid addition. After the addition is complete, thereaction mixture is allowed to slowly warm to room temperature withinthe water bath. The volume of the swollen polymer is approximately500-600 mL within the reactor. After warming to room temperature, thepolymer slurry is allowed to stand overnight without stirring. Theliquid layer is then removed from the polymer using a small-borecannula. The beads are then washed several times with dichloromethane.(The liquid layer and dichloromethane washes are slowly and carefullyquenched in a separate vessel using ice.) The polymer beads are thencarefully transferred to a fritted-glass funnel, and the polymer beadsare quenched by slow, careful addition of ice water.

After washing the beads extensively with water, excess solid sodiumbicarbonate is slowly added to a suspension of the polymer beads inwater. The mixture is allowed to stand overnight at room temperature.The polymer/sodium bicarbonate mixture is then heated to 50° C. for 2 h.The polymer slurry is allowed to stand at room temperature for 6 days.The polymer is light-colored and more highly swollen at this point. Theslurry is heated to 50° C. and allowed to react overnight, giving a pH 4solution of even more swollen polymer (approximately 600-700 mL volume).Addition of a small amount of sodium bicarbonate gives a pH 7 solution.

C. Thiolation

To the aqueous polymer bead slurry from above is added sodiumbicarbonate (60.5 g, 0.720 mol). The mixture is evacuated andback-filled with nitrogen three times. Thiolacetic acid (41.1 g, 0.540mol) is added slowly dropwise over 1 h 10 min to the polymer slurry atroom temperature. The mixture is slowly warmed to 80° C. over several hand allowed to react at 80° C. for 3 days. After cooling to 40° C., thesupernatant solution is removed using a small-bore cannula. The polymeris washed several times with water, giving slightly off-white coloredpolymer beads. Concentrated hydrochloric acid (250 mL) is added to thepolymer and the slurry is heated to 50° C. for 3 h. After cooling toroom temperature, the hydrochloric acid solution is removed using asmall-bore cannula. The polymer beads are then washed several times withdilute hydrochloric acid and the beads are transferred to afritted-glass funnel. The beads are again washed repeatedly with dilutehydrochloric acid followed by extensive washings with water, givingslightly off-white water-swollen beads. (The water-swollen volume of thepolymer beads is approximately 900 mL.) The beads are washed withmethanol (methanol-swollen volume approximately 600 mL) and finally withdichloromethane. After drying in a vacuum oven at 60° C. overnight, thedark-colored beads have a dry volume of approximately 200 mL. Thisproduct is identified as XEMSA-5C.

D. Preparation of Catalyst from Polystyrene and 11-bromo-1 -undecene(XEMSA-1C)

Catalyst is prepared as above, starting with macroporous polystyrene(Amberlite™ XE-305) and 11-bromo-1-undecene.

EXAMPLE 23

Evaluation of Polymeric Mercaptosulfonic Acid Catalysts

A. Evaluation of the Mercaptosulfonic Acid Polymer (XEMSA-5C) in theReaction of Phenol with Fluorenone

To a 4 dram vial equipped with a stirring bar is added 4.32 g of a20.8:1 molar ratio mixture of phenol to fluorenone and 0.26 g (6% byweight of the reactant solution) of the mercaptosulfonic acid polymer(XEMSA-5C) prepared as described in Example 22A-C. The reaction mixtureconsists of a homogeneous liquid phase plus a separate heterogeneouspolymer catalyst phase. The mixture is heated to 50° C. for 5 h. Thereaction is monitored throughout the reaction period by collectingsamples and analyzing by HPLC. The 9-fluorenone is found to be 36%consumed within 2 h and 76% consumed within 5 h. HPLC analysis(analytical method 3) gives the following relative area % analysis forthe products after 5 h of reaction (76% conversion):9,9-bis-(4-hydroxyphenyl)fluorene (97.45 area %):9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene (2.17 area %): adductcontaining two fluorene units and three phenolic units (0.39 area %).

B. Evaluation of the Mercaptosulfonic Acid Polymer (XEMSA) in theReaction of Phenol with Fluorenone

To a 4 dram vial equipped with a stirring bar is added 4.32 g of a20.8:1 molar ratio mixture of phenol to fluorenone and 0.26 g (6% byweight of the reactant solution) of the mercaptosulfonic acid polymer(XEMSA, degree of functionalization approximately 0.28 frombromoalkylation step) prepared as described in Example 20. The reactionmixture consists of a homogeneous liquid phase plus a separateheterogeneous polymer catalyst phase. The mixture is heated to 50° C.for 5 h. The reaction is monitored throughout the reaction period bycollecting samples and analyzing by HPLC. The 9-fluorenone is found tobe 44% consumed within 2 h and 75% consumed within 5 h. HPLC analysis(analytical method 3) gives the following relative area % analysis forthe products after 5 h of reaction (75% conversion):9,9-bis-(4-hydroxyphenyl)fluorene (96.10 area %):9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene (3.52 area %): adductcontaining two fluorene units and three phenolic units (0.38 area %).

C. Evaluation of Mercaptosulfonic Acid Polymer (PMBSA-MER) in theReaction of Phenol with Fluorenone

To a 4-dram vial equipped with a stirring bar is added 4.32 g of a20.8:1 molar ratio of phenol:fluorenone and 0.26 g (6% by weight of thereaction solution) of PMBSA-MER of Example 21C. The reaction mixtureconsists of a homogeneous liquid phase plus a separate heterogeneouspolymeric catalyst phase. The mixture is heated at 50° C. for 2 h. Thereaction is monitored by collecting samples, which are analyzed by HPLC.The 9-fluorenone is 99.5% consumed within 2 h. The product after 2 hcontains 96.83 area % of 9,9-bis-(4-hydroxyphenyl)fluorene, 2.44 area %of 9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene and 0.72 area % of anadduct containing two fluorene units and three phenolic units by HPLC(analytical method 3).

D. Evaluation of Mercaptosulfonic Acid Polymer (PMBSA-SU) for theReaction of Phenol with Fluorenone

To a 4-dram vial equipped with a stirring bar is added 4.32 g of a20.8:1 molar ratio mixture of phenol:fluorenone and 0.26 g (6% by weightof the reactant solution) of the polymer of Example 21B (PMBSA-SU). Thereaction mixture consists of a homogeneous liquid phase plus a separateheterogeneous polymer catalyst phase. The mixture is heated to 50° C.for 5 h. The progress of the reaction is followed by HPLC. At the end of2 h, 67% of the fluorenone is consumed, and 85% at the end of 5 h. Atthe end of 5 h, the reaction mixture contains 97.09 area % of9,9-bis-(4-hydroxyphenyl)fluorene, 2.25 area % of9-(2-hydroxyphenyl)-9-(4-hydroxyphenyl)fluorene and 0.66 area % of anadduct containing two fluorene units and three phenolic units by HPLCanalysis.

Results for the evaluation of various polymer mercaptosulfonic acids forcondensing phenol with fluorenone are given in Table X.

                  TABLE X                                                         ______________________________________                                        CONVERSION OF FLUORENONE (%) USING 6% BY                                        WEIGHT OF POLYMERIC CATALYSTS AT 50° C.                                              Reaction time (h)                                             Resin           0     2       4   5    7   18                                 ______________________________________                                        PMBSA-MER       0     99.5                                                      PMBSA-SU (PVBC) 0 67  85                                                      PMBSA (PVBC) 0 66                                                             XEMSA-5C 0 36  76                                                             (Amberlite ™ XE-305)                                                       XEMSA 0 49  75 82                                                             (Amberlite ™ XE-305)                                                       Dowex* 50 (DMT promoted) 0  17   73                                         ______________________________________                                         *Trademark of The Dow Chemical Company.                                  

EXAMPLE 24

Evaluation of the Mercaptosulfonic Acid Polymers in the Reaction ofPhenol with Acetone

To a 4 dram vial equipped with a stirring bar is added 4.33 g of a 14:1molar ratio mixture of phenol to acetone and 0.26 g (6% by weight of thereactant solution) of the appropriate mercaptosulfonic acid polymer. Thereaction mixture typically consists of a homogeneous liquid phase plus aseparate heterogeneous polymer catalyst phase. The mixture is heated toand allowed to react at 50° C. The reaction is monitored throughout thereaction period by collecting samples and analyzing by HPLC. HPLCanalysis (analytical method 3) shows the following acetone % conversiondata (based upon the quantity of bisphenol A produced) for the differentcatalysts are given in Table XI:

                  TABLE XI                                                        ______________________________________                                        % ACETONE CONVERSION                                                            (BASED UPON BISPHENOL A PRODUCED)                                                          Reaction time (h)                                              Resin          0.0   1.0     2.25 2.5   4.0 5.0                               ______________________________________                                        Dowex* 50wX4, 25% DMT                                                                        0             18         44                                      promoted                                                                      PMBSA (from uncross- 0  35  60 75                                             linked PVBC)                                                                  XEMSA-5C (DF ≈ 0.20) 0  38   82                                       XEMSA (DF ≈ 0.28) 0  23   32                                          PMBSA-SU 0  2   9                                                             PMBSA-MER (2% cross- 0 66  88                                                 linked, 200-400 mesh)                                                       ______________________________________                                         *Trademark of The Dow Chemical Company                                        DMT is 2,2dimethylthiazolidine                                           

EXAMPLE 25

A. Preparation of BHPF: Methylene Chloride Azeotrope to Remove Water;Precipitation from Methylene Chloride; 5.75:1 Molar Ratio of Phenol to9-fluorenone; Coprecipitation with Tetrachloroethylene

To a reactor (isothermal stirred batch reactor; reactor design 4) ischarged 75.0 g (0.80 mole) of phenol and 24.98 g (0.1386 mole) of9-fluorenone. The mixture is heated to 40° C. and catalyst (0.973 g,0.0062 mole, 3-mercaptopropanesulfonic acid) is charged to the reactor.Heating is continued. The course of the reaction is followed by HPLC(analytical method 3) At 30% conversion, methylene chloride (15 g) isadded to the reaction mixture so as to keep the mixture stirrable and touse a water/methylene chloride azeotrope (about 180 mm Hg, T=37° C.) toremove water of reaction. The reaction mixture is cooled at the end ofthe reaction (nearly complete fluorenone consumption, >99% oftheoretical water) to increase the amount of crystalline precipitate.

The progress of the run is given in Table XII.

The reaction mixture (˜97% selectivity to 4,4-BHPF, little unreactedfluorenone) is split into two parts. The first fraction (53.3 g) isfiltered. The filter cake is washed with methylene chloride (49 g) andthen with hot water (55 g). The recovery is 6.4 g (first crop) and 0.6 g(second crop) of white crystals, corresponding to 99% purity 4,4-BHPF(33% recovery).

To the remainder of the mixture (70.3 g) is added 61 g oftetrachloroethylene. The crystals are removed by filtration and thefilter cake is washed with 50 g of tetrachloroethylene and then with 115g of hot water. The recovered product weighs 11.5 g (43% recovery, 99%as 4,4-BHPF, white solid).

These results show that use of tetrachloroethylene, in combination withmethylene chloride, gives higher recovery of 99% pure 4,4-BHPF).

                  TABLE XII                                                       ______________________________________                                        Time    Temp.                                                                   h:min ° C. mm. Hg Observations, Actions                              ______________________________________                                        0:0     37      760      Add MPSA; turns orange, then dark                         green brown                                                                0:20 36 760 Color light brownish                                              0:40 36 760 Sample taken                                                      1:15 36 760 Seed crystal added                                                2:10 36 760 Sample taken                                                      2:28 36 760 Methylene chloride (15 g) and seed                                   crystal added; no crystallization;                                            temp. raised to 45° C.                                              2:30 37 ˜180 Sample taken; seed crystal not                                dissolving                                                                 3:10 45 ˜180 Heater set at 40° C.                                3:30 40 ˜180 Seed crystals added                                        3:50 40 ˜180 Mixture hazy                                               4:30 40 ˜180 Mixture hazy                                               5:10 40 ˜180 Sample taken                                               6:43 40 760 Vacuum turned off, stirrer speed                                     increased                                                                  9:30 40 760 Sample taken; methylene chloride                                     (˜20 g) added to mixture; stirrer                                       speed increased; heater turned off                                       ______________________________________                                    

B. Use of Methylene Chloride Azeotrope to Accelerate Reaction; 5.75:1Molar Ratio of Phenol to 9-fluorenone

To a reactor (reactor design 5) is charged 75.0 g (0.80 mole) of phenol,24.98 g (0.1386 mole) of 9-fluorenone and 15.0 g of methylene chloride.The mixture is heated to 40° C. Catalyst (3-mercaptopropanesulfonicacid, 0.757 g, 0.0049 mole) is charged to the reactor and the mixture isstirred. The reaction is followed by HPLC (analytical method 3).

At the end of the reaction, methylene chloride is added to produce amixture of about 30:30:˜30% by weight of methylene chloride:BHPF:phenoland the mixture is heated to dissolve the crystalline material.Additional methylene chloride is added to the solution and the solutionis cooled to promote crystalliza-tion.

The progress of the reaction is shown in Table XIII.

At the end of the reaction, half of the resulting mixture is filteredand the filter cake is washed with 64 g of methylene chloride. The firstcrop of BHPF weighs 7.0 g (dried overnight at 40° C.) and is white withvery little pink coloration. A second crop of crystals is collected andwashed with 28 g of methylene chloride. Weight, 4.1 g (dried overnightat 40° C., slightly pink), about 99% purity after a further washing withwater.

The remainder of the reaction mixture is filtered and the filter cake iswashed with methylene chloride and hot water and dried overnight at 40°C. The recovery is 14 g (51% overall recovery), about 99% purity byHPLC.

                  TABLE XIII                                                      ______________________________________                                        Time    Temp.                                                                   h:min ° C. mm. Hg Observations, Actions                              ______________________________________                                         0:0    45      760      Add MPSA, turns dark                                    0:09 45 760 Add about 20 g of methylene                                         chloride; color is dark                                                       brownish                                                                    0:30 45 760 Lighter brown; reduce                                               pressure to ˜180 mm                                                   1:00 45 ˜180 Seed crystal added; no                                       crystallization observed                                                    2:00 45 ˜180 Seed crystal added; no                                       crystallization observed                                                    3:00 45 ˜180 Sample taken; seed crystal                                   added; crystal not dissolving                                               3:45 45-> ˜180 Heater set at 40° C.; crystals                      forming                                                                     4:00 40 ˜180 More crystals forming                                      6:30 40  Sample taken; solid                                                    crystalline mass; stirring                                                    ineffective; yellowish color;                                                 vacuum turned off                                                          19:00 40 760 Sample taken; ˜50-70% of BHPF                                 crystallized; 33% by weight                                                   of methylene chloride added;                                                  temperature increased to 58° C.                                     ˜20:30 58 760 Temperature lowered to <40° C.;                       methylene chloride added to                                                   80% make up by weight of                                                      mixture                                                                     24 760 Cooled to room temperature                                          ______________________________________                                    

C. Reaction Using Methylene Chloride as Solvent: 3.5:1 Molar Ratio ofPhenol to Fluorenone

Phenol (30.0 g, 0.32 mole), 9-fluorenone (16.41 g, 0.0911 mole) and 15.0g of methylene chloride are charged to a reactor (reactor design 4). Themixture is stirred and heated at 40° C. and 1.122 g (0.0072 mole) ofMPSA is added over ˜1 min. Heating is continued at 41° C. for theduration of the reaction. The following observations are made during therun:

    ______________________________________                                                 Temp.                                                                  Time (h) (° C.) Observations, Actions                                ______________________________________                                        0        41        MPSA added; turns orange to brown to                           dark brown within about 30 sec                                              0.18 41 purple color                                                          0.5 41 sample taken                                                           1.5 41 sample taken                                                           1.67 41 orange mixture seeded with crystals                                   3 41 sample taken; heater off; left overnight                                 4 41 heater off                                                               6 room sample taken; ˜80% conversion; more                                2:3 adduct than 2,4 adduct                                                ______________________________________                                    

The crystalline solid is removed by filtration and the filter cake iswashed with methylene chloride. A second crop of crystals is recoveredfrom the mother liquors. The yield is 0.86 g (first crop), 8.66 g(second crop), 3.5 g (third crop), overall 13 g (41%), >99% purity byHPLC (method 3).

C. Phenol: Fluorenone Molar Ratio of b 15:1: MPSA Catalyst; PhenolRemoved by Distillation; Crystallized from Methylene Chloride

To a mixture of phenol and fluorenone (15:1 molar ratio), heated toabout 65° C., is added about 0.0498 equivalent of3-mercaptopropanesulfonic acid (with respect to fluorenone). Theresulting mixture is heated at about 65° C. for 2 h, after which thereaction mixture is washed with water (14 times the volume of themixture) to remove MPSA. The washed reaction mixture is distilled to aphenol:BHPF weight ratio of 1:1 and cooled to bring aboutcrystallization of BHPF. Crystalline material is removed by filtration,washed with methylene chloride, washed with water and dried to give BHPF(99.8% by weight of 4,4-isomer).

EXAMPLE 26

Condensation of Phenol and Acetone to Produce 2.2-bis-(4-hydroxyphenyl)Propane

A. Feed Containing 6% by Weight of Acetone, Plus Water, SolubleCatalyst; Batch Reaction

The reaction is carried out in a 2-L jacketed baffled resin pot,equipped with a condenser and nitrogen purge. Isothermal temperaturecontrol is provided by a fluid material, circulated through the reactorjacket. Stirring is provided by a Lightnin Labmaster TS2510 stirrer,equipped with an A-310 impeller.

To the reactor is charged 1200 g of feed, containing 90.0% by weight ofphenol, 6.0% by weight of acetone, 1.8% by weight of water and 2.2% byweight of MPSA. The mixture is heated at 35° C. At the end of 2 hours'heating, crystallization occurs in the reaction mixture. The reaction iscontinued 1 h more, at the end of which 80% of the acetone is reacted(HPLC). The reaction mixture is removed from the reactor and filtered.The weight of recovered crystals is 17%, consisting of a 1:1 adduct ofBPA:phenol (molar ratio). The crystalline adduct is washed with phenol.The washed adduct contains 57.7% by weight of 4,4-bisphenol, 160 ppm of2,4-bisphenol, 200 ppm of trisphenol, 2270 ppm of other tracebisphenolic impurities and 1170 ppm of MPSA, the balance being phenol.The mother liquor contains 8.44% by weight of 4,4-bisphenol, 0.26% byweight of 2,4-bisphenol, 0.13% by weight of trisphenol 0.62% by weightof other bisphenolic impurities, 0.81% by weight of acetone, 2.95% byweight of water and 2.78% by weight of MPSA, the balance being phenol.

B. Reaction Using Recycled Mother Liquors

The mother liquor from (A) is charged to a rotary evaporator withmake-up phenol (181 g). The evaporator is heated at 50° C. for about 30min, at the end of which the conversion of acetone is 90%. Pressure isreduced to 10 mm Hg absolute for 30 min, at the end of which the mixturecontains 1.4% by weight of water. The acetone content is below thedetection limit.

The dried mother liquor is returned to the reactor, along with make-upphenol, acetone, water and MPSA to give a mixture containing 92.0% byweight of phenol, 4.0% by weight of acetone, 1.8% by weight of water and2.2% by weight of MPSA. The total mass corresponds to (A), minus theweight of samples removed. The mixture is stirred and heated at 35° C.for 3 hr. Crystallization of BPA is observed after the initial 30 min ofheating. At the end of 3 hours' heating, acetone conversion is 80%. Thereaction mixture is processed as in (A). Recycling of the mother liquorsis repeated for 12 cycles. Results are given in Tables XIV and XV.

These experiments demonstrate that catalyst and unreacted materials canbe recovered and recycled without adversely affecting the process andthat results for successive runs are generally consistent andpredictable.

C. Reaction Using 10% by Weight of Acetone in the Feed with 3% by Weightof Water

An experiment is done as in (A), using 1200 g of feed, containing 85.5%by weight of phenol, 10.0% by weight of acetone, 3.0% by weight of waterand 2.2% by weight of MPSA. The reaction is done at 25° C. CrystallineBPA is visible after 13 h at this temperature. At the end of 24 h, theconversion of acetone is 40%.

Crystalline product, removed from the reaction mixture by filtration,constitutes 15% of the mixture. The crystals, a 1:1 adduct ofBPA:phenol, are washed with phenol. The washed crystals contain 51.8% byweight of the 4,4-isomer, 60 ppm of 2,4-isomer, <20 ppm of trisphenol,690 ppm of other trace bisphenols and 840 ppm of MPSA, the remainderbeing phenol. The mother liquors contains 6.73% by weight of 4,4-isomer,0.15% by weight of 2,4-isomer, 0.,08% by weight of trisphenol, 0.76% byweight of other bisphenols, 5.71% by weight of acetone, 4.97% by weightof water and 2.66% by weight of MPSA, the remainder being phenol.

                                      TABLE XIV                                   __________________________________________________________________________    COMPOSITION OF WASHED BISPHENOL A CRYSTALS                                                              Other                                                   4,4- 2,4- Tris- bis-                                                        Cycle Crystal isomer isomer phenol phenol MPSA                                No. % wt. % ppm ppm ppm ppm                                                 __________________________________________________________________________    1    17  57.7 160   200   2270  1170                                            2 22 60.4 420 n/d* 1730 1940                                                  3 17 59.7 460 270 2380 670                                                    4 18 60.7 560 260 2270 1440                                                   5 26 57.9 870 410 1840 1070                                                   6 18 59.3 790 330 2050 2110                                                   7 18 59.3 790 390 2150 740                                                    8 19 59.6 770 280 2100 750                                                    9 22 59.4 840 390 2000 860                                                    10   31 62.5 920 380 2210 1060                                                11  21 64.0 710 350 2020 1410                                                 12  23 63.0 770 280 1900 1500                                                 Avg. 22 ± 5 61 ± 2 800 ± 70 350 ± 50 2100 ± 100 1100                                         ± 300                                        Cycles                                                                        7-12                                                                        __________________________________________________________________________     *n/d = not detected                                                      

                                      TABLE XV                                    __________________________________________________________________________    MOTHER LIQUOR COMPOSITIONS                                                                         Other                                                       4,4- 2,4- Tris- bisphen-                                                     Cycle Isomer Isomer phenol olice Acetone Water MPSA                           No. wt % wt % wt % wt % wt % wt % wt %                                      __________________________________________________________________________    1   8.44 0.26  0.13  0.62  0.81 2.95 2.78                                       2 7.53 0.48 0.23 0.47 0.63 2.94 2.89                                          3 8.30 0.55 0.24 0.38 0.79 2.94 2.75                                          4 8.42 0.66 0.29 0.41 0.70 2.63 2.87                                          5 8.92 0.78 0.43 0.42 0.86 2.81 2.73                                          6 8.22 0.86 0.44 0.46 0.73 3.06 2.84                                          7 7.92 0.87 0.42 0.46 0.66 3.09 2.83                                          8 8.03 0.91 0.44 0.49 0.58 3.07 2.84                                          9 8.09 0.84 0.36 0.45 0.72 3.02 2.44                                          10   6.86 1.03 0.51 0.46 0.25 2.64 2.92                                       11  7.59 0.78 0.33 0.44 0.51 3.01 2.69                                        12  7.87 0.84 0.39 0.42 0.27 3.17 3.14                                        Avg. 7.7 ± 0.5 0.88 ± 0.09 0.41 ± 0.06 0.45 ± 0.02 0.5 ±                                          0.2 3.0 ± 0.2 2.8 ± 0.2                                                  Cycles                                    7-12                                                                        __________________________________________________________________________

EXAMPLE 27

Preparation of a Representative [(Mercaptoalkyl)(Sulfo)Phenylalkyl]Sulfonated Polystyrene Catalyst (Designated DPMSA-MER3C)

A. Alkylation

5.00 g sample of 200-400 mesh chloromethylated polystyrene/2%divinylbenzene co-polymer beads approximately 4.3 mmol Cl/g resin,approximately 64.5 mmole Cl) known in the art as a Merrifield resin(commercially available from Fluka Chemie AG) is added to a round bottomglass flask (reactor) under a pad of plant nitrogen with a sodiumhydroxide scrubber attached (to trap evolved HCl).(3-Bromopropyl)benzene (102.7 g, 78.4 mL, 8.0 equivalents) is added tothe dry resin beads. Dried (over 3 Angstrom molecular sieves)nitrobenzene (50 mL) is added, and the beads are slowly stirred at roomtemperature to allow for swelling of the beads. The reactor is cooled to0° C. in an ice water bath. A 20 mL sample of 1.0 M aluminum chloride innitrobenzene commercially available from Aldrich Chemical Co. is slowlyadded via syringe to the cold polymer slurry with rapid stirring overapproximately 10 minutes. The mixture turns dark red as soon as thealuminum chloride solution is added and exotherms to approximately 4° C.within the first 15 minutes of reaction with HCl being evolved from thesolution. After the addition of the AlCl₃ /nitrobenzene solution iscomplete, the mixture is slowly stirred at 0° C. for 2-3 hours, then isremoved to room temperature and slowly stirred overnight. The mixture isslowly poured onto ice to quench the aluminum chloride. Then the beadsare separated using a glass-fritted funnel with vacuum filtration. Thebeads are sequentially washed with water, acetone, dichloromethane,methanol, dilute aqueous hydrochloric acid, water and methanol, then aredried overnight in a vacuum oven at 70° C. (dry mass 23.52 g).

B. Sulfonation

The polymer beads from Example 27A (23.30 g, estimated 161.3 mmole ofphenyl groups) are added to a glass reactor with addition funnel andNaOH scrubber attached. Dichloromethane (100 mL) is added to the flaskand the beads are allowed to swell (rapid swelling is observed). Theslurry is cooled to 0° C. in an ice water bath. Chlorosulfonic acid(37.6 g, 21.4 mL, 320 mmole, approximately 2.0 equivalents perequivalent phenyl groups) is slowly added dropwise over approximately 2hours to the polymer slurry at 0° C. The mixture is allowed to slowlywarm to room temperature overnight in the water bath. The mixture isslowly poured onto ice to quench the excess chlorosulfonic acid, thenthe beads are separated using a glass-fritted funnel with vacuumfiltration. The beads are then washed extensively with water. Water isadded to make a slurry, then solid sodium bicarbonate is slowly added insmall portions over approximately 2 hours until no more bubbling isobserved (all active acid sites neutralized). The mixture is allowed tostand 3 days in the aqueous sodium bicarbonate solution (some additionalbead swelling observed over this time period). The beads are washed withwater and transferred to a glass reactor with 100 mL of water. The beadsare then heated to 70-80° C. over 2 hours to ensure hydrolysis of anyresidual sulfonyl chloride groups.

C. Thiolation

The aqueous polymer slurry from Example 27B is cooled to roomtemperature. Sodium bicarbonate is slowly added until the slurry isneutral (no bubbling observed), then additional sodium bicarbonate (27.1g, 323 mmol) is added to the aqueous bead slurry. Thiolacetic acid (24.6g, 23.1 mL, 323 mmol) is added to an addition funnel. The reactor isevacuated and refilled with nitrogen several times to minimize the aircontent. The thiolacetic acid is slowly added over approximately 15-20minutes to the aqueous bead slurry with rapid stirring. The additionrate is adjusted to control the effervescent evolution of carbon dioxidewhich is formed in the neutralization process. After the thiolaceticacid addition is complete, the mixture is heated to 70° C. and isallowed to react overnight with minimal stirring. The mixture is thencooled to room temperature and the beads are collected by filtrationusing a fritted-glass funnel. The beads are washed extensively withwater, then with dichloromethane, and then washed again with water. Thebeads are transferred back to the glass reactor, then concentrated (12molar) hydrochloric acid (100 mL) is added. The mixture is heated withmild stirring to 50° C. for 4-5 hours, then is cooled to roomtemperature. Deionized water (100 mL) is added and the beads are againcollected by filtration using a fritted-glass funnel. The beads arewashed with water, then are washed extensively (approximately 500 mL)with dilute (approximately 3 molar) aqueous hydrochloric acid. The beadsare then washed again with deionized water and finally are washed withmethanol to displace the water and shrink the polymer beads. The beadsare dried overnight in a vacuum oven at 70° C. (dry mass 34.17 g). Thefinal polymer catalyst is designated as DPMSA-MER3C

D. Preparation of Three-Carbon DPMSA Polymer from Merrifield Resin Beads

Another mercaptosulfonic acid polymer is prepared using the procedure ofsteps A-C of Example 27, except using a chloromethylated polystyreneresin (2% divinylbenzene, 200-400 mesh, approximately 4.3 mmol Cl/gresin), a Merrifield resin commercially available from Fluka Chemie AGas the polymeric support and (3-bromopropyl)benzene in the alkylationstep of the reaction. The resulting polymer is identified asDPMSA-MER3C.

E. Preparation of Three-Carbon DPMSA Polymer from ChloromethylatedGel-Resin Beads

Another mercaptosulfonic acid polymer is prepared using the procedure ofsteps A-C of Example 27, except using a chloromethylated 1.5%crosslinked polystyrene gel-resin (-30+70 mesh, approximately 4.3 mmolCl/g resin) as the polymeric support and (3-bromopropyl)benzene in thealkylation step of the reaction. This polymer is identified asDPMSA-1.5X3C.

F. Preparation of Two-Carbon DPMSA Polymer from ChloromethylatedGel-Resin Beads

Another mercaptosulfonic acid polymer is prepared using the procedure ofsteps A-C of Example 27, except using a hloromethylated 1.5% crosslinkedpolystyrene gel-resin (-0+70 mesh, approximately 4.3 mmol Cl/g resin) asthe polymeric support and (2-bromoethyl)benzene in the alkylation stepof the reaction. This polymer is identified as DPMSA-1.5X2C.

G. Preparation of three Carbon DPMSA from 6% Crosslinked MacroporousResin

Another mercaptosulfonic acid polymer is using the procedure of stepsA-C of Example 27, except using a chloromethylated 6% crosslinkedmacroporous polystyrene resin (approximately 30-70 mesh, approximately4.3 mmol Cl/g resin) as the polymeric support and (3-bromopropyl)benzenein the alkylation step of the reaction. This polymer is identified asDPMSA-6/42-3C.

H. Preparation of three Carbon DPMSA from 6.5% Crosslinked Gel Resin

Another mercaptosulfonic acid polymer is using the procedure of stepsA-C of Example 27, except using a chloromethylated 6.5% crosslinkeduniform particle size polystyrene gel-resin (380 micron, approximately4.3 mmol Cl/g resin) as the polymeric support and (3-bromopropyl)benzenein the alkylation step of the reaction. This polymer is identified asDPMSA-6.5X3C.

EXAMPLE 28

Evaluation of Catalysts in Continuous Processes

A fixed bed downflow reactor, having a volume of 10-mL, is constructedfrom a vertical tube, filled with catalyst. External to the catalyst bedis a preheater area, packed with glass wool. Ancillary equipmentincludes a pressure regulator, relief valve, pump and heater for thefeed. The feed is heated by heating fluid, circulated through the feedpot, and is kept under a nitrogen pad.

The feed is phenol (99.9%) and fluorenone (˜99%) in a 21:1 molar ratio.

The heating fluid, heating tape and reactor are turned on. The selectedcatalyst is slurried in phenol at ˜45° C. Catalyst-phenol mixture ispipetted into the reactor, at the bottom of which a plug of glasswool/glass beads is placed to prevent catalyst from leaving the reactor.The phenol:fluorenone is added to the feed pot at 55° C. The pressure isadjusted to ˜0.34 bars.

Phenol:fluorenone feed is introduced into the reactor and thecomposition of the effluent from the reactor is followed by HPLC.

The following results are obtained:

                  TABLE XVI                                                       ______________________________________                                        conversion   % fluorenone                                                       time (h) conversion                                                         ______________________________________                                        PMBSA-Mer catalyst (Example 9C) at 50° C.:                               productivity 1.4 g BHPF/g cat h                                                     0.33     99.7                                                           28 100.0                                                                      53 100.0                                                                      69 99.7                                                                       89 99.9                                                                       113 100.0                                                                     137 99.8                                                                      144 99.6                                                                      162 99.6                                                                     selectivity 98% 4,4BHPF                                                  

    PMBSA-XEBr (Example 9D) at 69° C.:                                       productivity 0.6 g BHPF/g cat h                                                     2        99.8                                                           15 100.0                                                                      39 100.0                                                                      63 98.9                                                                       79 99.0                                                                       103 95.5                                                                      127 87.1                                                                      164 83.4                                                                     selectivity 98% 4,4BHPF                                                  

    PMBSA-XEC1 (Example 9E) at 56° C.:                                       productivity 1.48 g BHPF/g cat h                                                    2        99.2                                                           27 99.1                                                                       63 99.3                                                                       87 98.7                                                                       111 98.9                                                                      135 98.6                                                                      159 98.3                                                                      164 98.0                                                                     selectivity 98% 4,4BHPF                                                  

    XEMSA-11C (Example 22D) at 60° C.:                                             1        99.2                                                           17 94.4                                                                       41 92.2                                                                       65 91.0                                                                     DPMSA-MER3C (Example 27D) at 50° C.:                                     productivity 4 lb BHPF/lb catalyst/hour = 4 kg/kg/h                                 20       99.9                                                           24 99.9                                                                       39 99.9                                                                       48 100.0                                                                      66.5 100.0                                                                    75.5 98.9                                                                     99.5 99.1                                                                     103 98.6                                                                      104 98.7                                                                     selectivity 98% p,pBHPF                                                  

    XEMSA-5C (Example 22) at 55° C.:                                         productivity 0.43 lb BHPF/lb catalyst/hour = 0.43 kg/kg/h                           4        99.7                                                           22 100.0                                                                      46 100.0                                                                      70 100.0                                                                      77 99.7                                                                       94 99.7                                                                       118 99.7                                                                      142 99.5                                                                      144 99.4                                                                      168 99.3                                                                      192 99.0                                                                      216 99.0                                                                      240 98.6                                                                      264 98.6                                                                     selectivity 98% p,pBHPF                                                  

    DPMSA-XE3C (Example 27A-C) at 56° C.:                                          30       98.0                                                           48 95.1                                                                       72 94.7                                                                       96 92.3                                                                       123 87.3                                                                      144 86.1                                                                      170 83.8                                                                      240 77.1                                                                    selectivity 98% p,p-BHPF                                                      ______________________________________                                    

These results show that PMBSA, XEMSA, and DPMSA catalysts of theinvention can exhibit stability over time, thus, have very usefullifetimes.

EXAMPLE 29

Continuous Process for Making BHPF Using Mercaptopropanesulfonic AcidCatalyst

The reactor comprises a three-staged continuous reactor (isothermalperfectly stirred type). The reaction is run at 46° C. at a 21:1 molarratio of phenol:fluorenone (98%, Aldrich), the amount of MPSA being0.05-0.07 equivalent of MPSA:mole of fluorenone. The composition of theproducts is followed by HPLC.

The reaction is continued for 228 h, at the end of which fluorenoneconversion is 99.95% (reactor 2) or 99.9% (reactor 1) and selectivity to4,4-BHPF is 98.32% (reactor 2) or 95.2% (reactor 1).

EXAMPLE 30

Evaluation of Catalyst of Example 22D (XEMSA-5C) in Continuous Processfor Making Bisphenol A

The reactor comprises a vertical upflow column of stainless steeltubing, packed with resin atop a screen and glass beads. The column isheated by a water jacket. The progress of the reaction is followed asabove by HPLC.

The following results are obtained:

                  TABLE XVII                                                      ______________________________________                                                      25% promoted XEMSA-5C                                             Test Dowex ™ 50Wx4 Example 22D                                           ______________________________________                                        Acid capacity                                                                   dry meq/g 4.0 3.5                                                             wet meq/mL 0.84 1.17                                                          Swell test 0.55 0.72                                                          phenol/water vol.                                                             Reaction tests                                                                30 min res. time                                                              4% acetone, 65° C.                                                     4,4 % by wt 12.7 14.0                                                         conversion 0.83 >0.95                                                       productivity  8.2          9.0 ± 0.2                                         2,4/4,4 0.28 0.024 ± 0.001                                                 6% acetone, 65° C.                                                     4,4 % by wt ˜15 19.1 ± 0.6                                         conversion    ˜0.7   0.92                                               productivity  ˜10    12.2 ± 0.4                                        2,4/4,4 ˜0.27 0.025 ± 0.003                                          4% acetone, 55° C.                                                     4,4 10.7 13.0 ± 0.1                                                        conversion 0.67 0.92 ± 0.01                                                productivity 7.2  8.3 ± 0.06                                               2,4/4,4 0.21 0.019 ± 0.001                                               ______________________________________                                    

EXAMPLE 31

Preparation of Bisphenol F

Phenol and formaldehyde are reacted to produce bisphenol F. Similarresults are obtained.

The preceding examples can be repeated with similar success bysubstituting the generically or specifically described reactants and/oroperating conditions of this invention for those used in the precedingexamples.

From the foregoing description, one skilled in the art can easilyascertain the essential characteristics of this invention and withoutdeparting from the spirit and scope thereof, can make various changesand modifications of the invention to adapt it to various usages andconditions.

EXAMPLE 32

Alternate Preparation of a Representative[(Mercaptoalkyl)(Sulfo)-Phenylalkyl] Sulfonated Polystyrene Catalyst(Designated DPMSAA-0.25-1.5X2C)

A Preparation of (2-Bromoethyl)benzyl Chloride

(A1) In an extension of the procedure described by Selva, M; Trotta, F.;and Tundo, P. Synthesis, 1991, 1003-1004, (2-bromoethyl)benzylchlorideis prepared by the following procedure:

Concentrated sulfuric acid (132 mL) is slowly added to ice colddeionized water (66 mL) in a 1 L three-necked glass reactor fitted witha mechanical stirrer, reflux condenser, and temperature probe. Thereactor containing the sulfuric acid solution is cooled in an ice bath,then (2-bromoethyl)benzene (92.5 g, 0.50 mol) is added followed by 50percent tetrabutylammonium chloride in water (10 g of solution),paraformaldehyde (20.0 g, 0.666 mol, 1.33 equivalents), and finallysodium chloride (80.0 g, 1.37 mol, 2.74 equivalents). The slurry isstirred at approximately 1000 rpm (very vigorous) and heated to 80° C.for 2.25 hours. The reaction is less than 50 percent complete asdetermined by gas chromatographic analysis. Additional paraformaldehyde(20.0 g, 0.666 mol, 1.33 equivalents) is added and the mixture isstirred (600-700 rpm) an additional 3.5 hours at 80° C. The reaction isapproximately 50 percent complete as determined by gas chromatographicanalysis. The mixture is allowed to cool and is transferred to aseparatory funnel. The organic phase is separated and saved for furtherreaction.

(A2) Alternatively, (2-Bromoethyl)benzene (92.5 g, 0.50 mol),concentrated (12 molar) hydrochloric acid (125 mL, 1.5 mole HCl, 3equivalents HCl), and paraformaldehyde (22.5 g, 0.75 mol, 1.5equivalents) are added to a 1 L three-necked glass reactor fitted with amechanical stirrer, addition funnel, and temperature probe. Concentratedsulfuric acid (111 mL, approximately 205 g, approximately 4 equivalentsof sulfuric acid) is added to the addition funnel. A small portion(approximately 10-15 mL) of the sulfuric acid is added to the reactionmixture from the addition funnel and the slurry is heated to 80° C. withstirring at approximately 1000 rpm. After the reaction reaches 80° C.,the remaining concentrated sulfuric acid is added dropwise over 3 hours.After an addition 1 hour reaction time, the reaction is less than 50percent complete as determined by gas chromatographic analysis. Themixture is allowed to cool and is transferred to a separatory funnel.The organic phase is separated and saved for further reaction.

The combined products from Example 32, parts A1 and A2 containingunreacted (2-bromoethyl)benzene and chloromethylated(2-bromoethyl)benzene products (mixture of isomers) are furtherchloromethylated according to the procedure described in part A1. Thereaction is performed using sufficient time and reagent(paraformaldehyde, sodium chloride, sulfuric acid) charges to completelyconsume the (2-bromoethyl)benzene starting material, giving a mixture of(2-bromoethyl)benzyl chloride isomers along with higher-boilingby-products. The mixture of (2-bromoethyl)benzyl chloride isomers isisolated by oil-pump vacuum bulb-to-bulb Kugelrohr distillation (up to140-145° C.). The isolated product is a water-white oil which solidifiesupon standing at room temperature. Gas chromatography analysis showsthat unreacted (2-bromoethyl)benzene and the higher boiling by-productsare essentially absent from the distilled (2-bromoethyl)benzyl chlorideisomers product.

B. Alkylation

Styrene/divinylbenzene co-polymer resin beads (10.00 g, -30+70 mesh, 1.5percent divinylbenzene, approximately 96.0 mmole styrene repeat units)are added to a round bottom glass flask (reactor) under a pad ofnitrogen with a sodium hydroxide scrubber attached (to trap evolvedHCl). A solution of (2-bromoethyl)benzyl chloride (mixture of aromaticring isomers, predominately para) (10.0 g, 0.238 equivalents based uponstyrene repeating units) in 1,2-dichloroethane (25 mL) is added to thedry resin beads. The beads are allowed to swell for approximately 5-10minutes, then additional 1,2-dichloroethane (35 mL) is added to theswollen beads. Anhydrous tin(IV) chloride (2.5 mL, approximately 5.57 g,approximately 21.4 mmol) is slowly added via syringe to the polymerslurry at room temperature over approximately 10 minutes with rapidstirring. The mixture turns light yellow when the tin(IV) chloride isadded. The mixture is slowly warmed (in 5° C. increments) to 40° C. overapproximately 30 minutes and is allowed to react at 40° C. for 1 hour.At this time the light orange mixture is slowly warmed (in 5° C.increments) to 60° C. over approximately 1 hour 30 minutes and isallowed to react overnight at 60° C. with slow stirring. After overnightreaction, the mixture is cooled to room temperature and is quenched byslowly adding methanol to the well-stirred polymer slurry. The beads areseparated from the solution using a glass-fritted funnel with vacuumfiltration. The beads are sequentially washed (three portions each) withdichloromethane, water, tetrahydrofuran, and methanol, then the beadsare dried overnight in a vacuum oven at 80° C. (dry mass 13.89 g).Theoretical mass yield=14.49 g. Alkylation yield (by mass uptake)=87percent. Approximate degree of polymer functionalization (by massyield)=0.21.

C. Sulfonation

The polymer beads from Example 32B (13.89 g, estimated 116 mmole ofphenyl groups) are added to a glass reactor with addition funnel andNaOH scrubber attached. Dichloromethane (75 mL) is added to the flaskand the beads are allowed to swell (rapid swelling is observed). Theslurry is cooled to approximately 3-5° C. in an ice water bath.Chlorosulfonic acid (11.7 mL, approximately 20.5 g, approximately 176mmol, approximately 1.5 equivalents per equivalent of phenyl groups) isslowly added dropwise over approximately 30 minutes to the cold polymerslurry with stirring. The mixture is allowed to react at approximately3-5° C. in an ice water bath for 1 hour. The mixture is removed from theice bath and allowed to warm to room temperature over 2 hours 45minutes. At this time, the polymer slurry is again cooled to 3-5° C. inan ice water bath, and water is slowly added with rapid stirring toquench the excess chlorosulfonic acid. The beads are separated using aglass-fritted funnel with vacuum filtration. The beads are then washedextensively with water. Water is added to make a slurry, then solidsodium bicarbonate is slowly added in small portions with stirring untilno more bubbling is observed (all active acid sites are neutralized).The beads are washed with water and transferred back to the glassreactor with 100 mL of water. The beads are then heated to 60-70° C.over 2 hours to ensure hydrolysis of any residual sulfonyl chloridegroups.

D. Thiolation

The aqueous polymer slurry from Example 32C (estimated approximately 20mmole Br) is cooled to room temperature. Sodium bicarbonate is slowlyadded until the slurry is neutral (no bubbling observed), thenadditional sodium bicarbonate (5.30 g, 63.0 mmol, approximately 3equivalents relative to estimated bromine content in beads) is added tothe aqueous bead slurry. Thiolacetic acid (4.5 mL, approximately 4.8 g,approximately 63 mmol, approximately 3 equivalents relative to estimatedbromine content in beads) is added to an addition funnel. The reactor isevacuated and refilled with nitrogen several times to minimize the aircontent. The thiolacetic acid is slowly added over approximately 10-15minutes to the aqueous bead slurry at room temperature with rapidstirring. The thiolacetic acid addition rate is adjusted to control theeffervescent evolution of carbon dioxide which is formed in theneutralization process. After the thiolacetic acid addition is complete,the mixture is heated to 70° C. and is allowed to react overnight withminimal stirring. The mixture is then cooled to room temperature and thebeads are collected by filtration using a fritted-glass funnel. Thebeads are washed extensively with water, then with dichloromethane(optional), and then washed again with water. The beads are transferredback to the glass reactor, then concentrated (12 molar) hydrochloricacid (100 mL) is added. The mixture is heated with mild stirring to 50°C. for 2-3 hours, then is cooled to room temperature. Deionized water(100 mL) is added and the beads are again collected by filtration usinga fritted-glass funnel. The beads are washed with water, then are washedextensively (approximately 500 mL) with dilute (approximately 3 molar)aqueous hydrochloric acid. The beads are then washed again withdeionized water and are transferred to a storage bottle without anyadditional drying. The final polymer catalyst has a titrated water-wet(water swollen) acid capacity of 0.80 milliequivalent/mL catalyst. Thefinal polymer catalyst is designated as DPMSAA-0.25-1.5X2C

E. Preparation of DPMSAA Resin with 0.71 Equivalents Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usingthe procedure described in steps B-D of Example 32, except using 0.71equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.Chlorosulfonic acid (2.0 equivalents relative to the calculated totalequivalents of phenyl groups in the polymer) is used in the sulfonationreaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents ofeach reagent relative to the calculated amount of bromine in thepolymer) are used in the thiolation reaction. The mass yield of polymerobtained from the alkylation reaction corresponds to a 83 percent yieldin the alkylation reaction and a degree of functionality of 0.59. Thefinal polymer catalyst has a titrated water-wet (water swollen) acidcapacity of 0.94 milliequivalent/mL catalyst. The final polymer catalystis designated as DPMSAA-0.75-1.5X2C.

F. Preparation of DPMSAA Resin with 0.43 Equivalents Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usingthe procedure described in steps B-D of Example 32, except using 0.43equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.Chlorosulfonic acid (2.0 equivalents relative to the calculated totalequivalents of phenyl groups in the polymer) was is in the sulfonationreaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents ofeach reagent relative to the calculated amount of bromine in thepolymer) are used in the thiolation reaction. The mass yield of polymerobtained from the alkylation reaction corresponds to a 81 percent yieldin the alkylation reaction and a degree of functionality of 0.35. Thefinal polymer catalyst has a titrated water-wet (water swollen) acidcapacity of 0.85 milliequivalent/mL catalyst. The final polymer catalystis designated as DPMSAA-0.45-1.5X2C.

G. Preparation of DPMSAA with 0.095 Equivalents Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usingthe procedure described in steps B-D of Example 32, except using 0.095equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.Chlorosulfonic acid (1.5 equivalents relative to the calculated totalequivalents of phenyl groups in the polymer) is used in the sulfonationreaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents ofeach reagent relative to the calculated amount of bromine in thepolymer) are used in the thiolation reaction. The mass yield of polymerobtained from the alkylation reaction corresponds to a 99 percent yieldin the alkylation reaction and a degree of functionality of 0.094. Thefinal polymer catalyst has a titrated water-wet (water swollen) acidcapacity of 0.80 milliequivalent/mL catalyst. The final polymer catalystis designated as DPMSAA-0.10-1.5X2C.

H. Preparation of DPMSAA with 0.42 Equivalents of(2-Bromoethyl)benzylchloride Alkylation and 0.30 Equivalents of BenzylChloride Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usingthe procedure described in steps B-D of Example 32, except using 0.42equivalents of (2-bromoethyl)benzyl chloride and 0.30 equivalents ofbenzyl chloride in the alkylation reaction. Chlorosulfonic acid (2.0equivalents relative to the calculated total equivalents of phenylgroups in the polymer) is used in the sulfonation reaction. Thiolaceticacid and sodium bicarbonate (3.0 equivalents of each reagent relative tothe calculated amount of bromine in the polymer) are used in thethiolation reaction. The final polymer catalyst has a titrated water-wet(water swollen) acid capacity of 0.94 milliequivalent/mL catalyst. Thefinal polymer catalyst is designated as DPMSAA-0.45/0.30-1.5X2C.

I. Preparation of DPMSAA Resin having 0.423 Equivalents Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usingthe procedure of steps B-D of Example 32, except using 0.423 equivalentsof (2-bromoethyl)benzyl chloride in the alkylation reaction and directlycarrying the polymer slurry obtained from the alkylation reactiondirectly on to the sulfonation reaction without any quenching.isolation, or washing steps after the alkylation reaction.Chlorosulfonic acid (1.25 equivalents relative to the total equivalentsof phenyl groups present in all reactants) is added directly to thepolymer slurry after the alkylation reaction is complete. Workup andsubsequent isolation of the product after sulfonation is as in Example32, except that more extensive washing is required to remove solublereaction by-products from the polymer slurry. Thiolacetic acid andsodium bicarbonate (3.0 equivalents of each reagent relative to theestimated maximum amount of bromine present in the polymer) are used inthe thiolation reaction. The final polymer catalyst has a titratedwater-wet (water swollen) acid capacity of 0.78 milliequivalent/mLcatalyst. The final polymer catalyst is designated asDPMSAA-0.45NW-1.5X2C.

J. Preparation of DPMSAA Resin with 0.238 Equivalents Alkylation

Another mercaptosulfonic acid polymer is prepared from 1.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (-30+70 mesh) usinga variation of the procedure described in Example 32. The alkylation andsulfonation reactions are performed in one step utilizing chlorosulfonicacid as the alkylation catalyst and sulfonation reagent.

Styrene/divinylbenzene co-polymer resin beads (10.00 g, -30+70 mesh,1.5% divinylbenzene, approximately 96.0 mmol styrene repeat units) areadded to a round bottom glass flask (reactor) under a pad of plantnitrogen with a sodium hydroxide scrubber attached (to trap evolvedHCl). A solution of (2-bromoethyl)benzyl chloride (mixture of aromaticring isomers, predominately para) (5.32 g, 0.238 equivalents based uponstyrene repeat units) in 1,2-dichloroethane (25 mL) is added to the dryresin beads. The beads are allowed to swell for approximately 5-10minutes, then additional 1,2-dichloroethane (35 mL) is added to theswollen beads. The slurry is cooled 2-3° C. in an ice bath, thenchlorosulfonic acid (12.0 mL, approximately 21.0 g, 1.5 equivalentsbased upon total equivalents of phenyl groups in the mixture) is addedslowly dropwise over approximately 1 hour 45 minutes. The mixture isallowed to stir an additional 1 hour at 3-4° C., then is removed to roomtemperature and allowed to react an additional 1.5 hours. The mixture isthen cooled in an ice water bath and water is slowly added to quench theexcess chlorosulfonic acid. Thereafter the beads are isolated accordingto the procedure described in part C of Example 32. Likewise, thethiolation reaction is as in part D of Example 32 using thiolacetic acidand sodium bicarbonate (3.0 equivalents of each reagent relative to theestimated maximum amount of bromine in the polymer). The final polymercatalyst has a titrated water-wet (water swollen) acid capacity of 0.94milliequivalent/mL catalyst. The final polymer catalyst is designated asDPMSAA-2S-0.25-1.5X2C.

K. Preparation of DPMSAA Resin Having 6.5 percent Crosslinking

Another mercaptosulfonic acid polymer is prepared from 6.5 percentcrosslinked styrene/divinylbenzene co-polymer beads (380 micron uniformparticle size spheres) using the procedure described in steps B-D ofExample 32, except using 0.427 equivalents of (2-bromoethyl)benzylchloride in the alkylation reaction. Chlorosulfonic acid (1.5equivalents relative to the calculated total equivalents of phenylgroups in the polymer) is used in the sulfonation reaction. Thiolaceticacid and sodium bicarbonate (3.0 equivalents of each reagent relative tothe calculated amount of bromine in the polymer) are used in thethiolation reaction. The mass yield of polymer obtained from thealkylation reaction corresponds to a 57 percent yield in the alkylationreaction and a degree of functionality of 0.24. The final polymercatalyst has a titrated water-wet (water swollen) acid capacity of 1.75milliequivalent/mL catalyst. The final polymer catalyst is designated asDPMSAA-0.45-6.5X2C.

L. Preparation of DPMSAA Resin with 0.25 Equivalents Alkylation andHaving 1.8% Crosslinking

Another mercaptosulfonic acid polymer is prepared from 1.8% crosslinkedstyrene/divinylbenzene co-polymer beads (-25+40 mesh) using theprocedure described in steps B-D of Example 32, except using 0.25equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.Chlorosulfonic acid (1.5 equivalents relative to the calculated totalequivalents of phenyl groups in the polymer) is used in the sulfonationreaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents ofeach reagent relative to the calculated amount of bromine in thepolymer) are used in the thiolation reaction. The mass yield of polymerobtained from the alkylation reaction corresponds to an 86% yield in thealkylation reaction and a degree of functionality of 0.22. The finalpolymer catalyst has a titrated water-wet (water swollen) acid capacityof 0.85 milliequivalent/mL catalyst. The final polymer catalyst isdesignated as DPMSAA-0.25-1.8X2C.

M. Preparation of DPMSAA Resin with 0.10 Equivalents Alkylation andHaving 1.8% Crosslinking

Another mercaptosulfonic acid polymer is prepared from 1.8% crosslinkedstyrene/divinylbenzene co-polymer beads (-25+40 mesh) using theprocedure described in steps B-D of Example 32, except using 0.10equivalents of (2-bromoethyl)benzyl chloride in the alkylation reaction.Chlorosulfonic acid (1.5 equivalents relative to the calculated totalequivalents of phenyl groups in the polymer) is used in the sulfonationreaction. Thiolacetic acid and sodium bicarbonate (3.0 equivalents ofeach reagent relative to the calculated amount of bromine in thepolymer) are used in the thiolation reaction. The final polymer catalysthas a titrated water-wet (water swollen) acid capacity of 0.81milliequivalent/mL catalyst. The final polymer catalyst is designated asDPMSAA-0.10-1.8X2C.

N. Preparation of 1.5% Crosslinked DPMSAA Resin with 0.10 EquivalentsAlkylation and Using Sodium Hydrosulfide in the Thiolation Reaction

Another mercaptosulfonic acid polymer is prepared from 1.5% crosslinkedstyrene/divinylbenzene co-polymer beads (-30+70 mesh) using a variationof the procedure described in steps B-D of Example 32, except using 0.10equivalents of (2-bromoethyl)benzyl chloride in the alkylation reactionand sodium hydrosulfide in the thiolation reaction. Chlorosulfonic acid(1.5 equivalents relative to the calculated total equivalents of phenylgroups in the polymer) is used in the sulfonation reaction. Sodiumhydrosulfide (6.4 equivalents relative to the calculated amount ofbromine in the polymer) is used in the thiolation reaction. The massyield of polymer obtained from the alkylation reaction corresponds to adegree of functionality of 0.10. The final polymer catalyst has atitrated water-wet (water swollen) acid capacity of 0.82milliequivalent/mL catalyst. The final polymer catalyst is designated asDPMSAA-AT-0.10-1.5X2C.

O. Preparation of DPMSAA Resin with 0.25 Equivalents Alkylation andHaving 4% Crosslinking

Another mercaptosulfonic acid polymer is prepared from 4% crosslinkedstyrene/divinylbenzene co-polymer beads (360 micron uniform particlesize spheres) using the procedure described in steps B-D of Example 32,except using 0.25 equivalents of (2-bromoethyl)benzyl chloride in thealkylation reaction. Chlorosulfonic acid (1.5 equivalents relative tothe calculated total equivalents of phenyl groups in the polymer) isused in the sulfonation reaction. Thiolacetic acid and sodiumbicarbonate (3.0 equivalents of each reagent relative to the calculatedamount of bromine in the polymer) are used in the thiolation reaction.The mass yield of polymer obtained from the alkylation reactioncorresponds to a 73% yield in the alkylation reaction and a degree offunctionality of 0.18. The final polymer catalyst is designated asDPMSAA-0.25-4X2C.

P. Preparation of DPMSAA Resin with 0.10 Equivalents Alkylation andHaving 4% Crosslinking

Another mercaptosulfonic acid polymer is prepared from 4% crosslinkedstyrene/divinylbenzene co-polymer beads (360 micron uniform particlesize spheres) using the procedure described in steps B-D of Example 32,except using 0.10 equivalents of (2-bromoethyl)benzyl chloride in thealkylation reaction. Chlorosulfonic acid (1.5 equivalents relative tothe calculated total equivalents of phenyl groups in the polymer) isused in the sulfonation reaction. Thiolacetic acid and sodiumbicarbonate (3.0 equivalents of each reagent relative to the calculatedamount of bromine in the polymer) are used in the thiolation reaction.The mass yield of polymer obtained from the alkylation reactioncorresponds to an 74% yield in the alkylation reaction and a degree offunctionality of 0.074. The final polymer catalyst is designated asDPMSAA-0.10-4X2C.

EXAMPLE 33

Evaluation of Catalysts in a Continuous Process

A three-stage up-flow reactor is constructed from three verticalstainless steel tubes with sampling ports between each section. Eachreactor stage is water jacketed for temperature control with allconnecting lines heat-traced to prevent reactor line plugging. Likewisethe 2L reactor feed tank is jacketed so that precise control of thereactor feed can be obtained. From the feed tank, feed flows through anelectrically heat-traced section of tubing for control of feed inputtemperature.

Each reactor section is packed with 10-20 mL of water-wet catalyst.

The reactor feed consists of a solution of 4 weight percent acetone inphenol. The acetone:phenol mixture is precisely metered into thetemperature controlled reactor system at a defined combination of flowrate (1.0 mL/min to 2.0 mL/min) and reactor temperature (55° C. to 65°C.). Upon start-up of each new loading of catalyst, the feed passesthrough the catalyst for at least 12 hours before measurements arerecorded to remove water from the catalyst. Product composition of thereactor effluent from each of the three stages is analyzed by HPLC whilegas chromatography is used to analyze for acetone and water. The resultsobtained from tests of the catalysts at various times of reaction(reactor residence times) are provided in Table XIX. Productivity isexpressed in terms of pounds of bisphenol A produced per hour per cubicfoot of water-swollen catalyst charged into the reactor. (NOTE: Unlessotherwise noted, all of the catalyst results are obtained at 55° C.)

                                      TABLE XIX                                   __________________________________________________________________________                    Res.                                                                             Acetone                                                                            Prod.                                                                             op/pp                                                                             tris/pp                                                                           Cyclics/pp                                                                         tot imp/pp                             CATALYST Time Conv.(%) lb/hr/ft3 (%) (%) (%) (%)                            __________________________________________________________________________    65 C DOWEX 50Wx4, 25% Prom.                                                                   10 61.47%                                                                             18.03                                                                             2.524%                                                                            0.702%                                                                            0.535%                                                                             5.393%                                  20 77.69% 11.53 2.722% 0.648% 0.472% 5.204%                                   30 84.52% 8.34 2.826% 0.628% 0.455% 5.149%                                   55 C DOWEX 50Wx4, 25% Prom. 10 49.28% 13.83 1.983% 0.783% 0.328% 5.297%        20 66.16% 9.51 2.102% 0.675% 0.292% 4.862%                                    30 73.02% 7.06 2.163% 0.692% 0.257% 4.838%                                   DPMSA-MER3C 5 84.28% 49.76 1.479% 0.549% 0.879% 5.053%                         10 97.63% 29.92 1.456% 0.491% 0.828% 3.829%                                   15 100.00% 20.62 1.449% 0.553% 0.836% 3.831%                                 DPMSA-1.5x3C 7.5 46.34% 18.12 1.884% 0.855% 0.929% 5.803%                      15 71.71% 14.51 1.769% 0.794% 0.890% 4.359%                                   22.5 81.41% 11.21 1.733% 0.730% 0.819% 4.951%                                DPMSA-1.5x2C 7.5 44.74% 16.13 1.577% 0.958% 1.524% 7.512%                      15 74.84% 14.31 1.537% 0.800% 1.298% 4.840%                                   22.5 88.14% 11.53 1.534% 0.790% 1.167% 5.372%                                DPMSA-6/42-3C 7.5 11.34% 3.08 2.519% 0.000% 2.096% 12.918%                     15 29.62% 4.38 2.203% 0.383% 2.044% 15.295%                                   22.5 52.79% 6.12 1.946% 0.296% 1.999% 12.032%                                DPMSA-6.5x3C 7.5 1.68% 0.13 0.000% 3.029% 0.000% 1.290%                        15 1.11% 0.05 0.000% 2.166% 0.000% 2.166%                                     22.5 0.34% 0.10 0.524% 0.687% 0.000% 0.671%                                  DPMSAA-0.75-1.5x2C 7.5 90.84% 34.65 1.583% 0.992% 0.570% 4.298%                                                       (0.75 funct.) 15 98.43% 20.02                                                1.596% 0.912% 0.513% 3.707%                                                     22.5 100.00% 13.30 1.521%                                                   0.922% 0.677% 3.478%                   DPMSAA-0.75-1.5x2C (2ML) 3.75 66.83% 51.95 1.571% 0.886% 0.687% 5.074%                                                 7.5 89.68% 35.41 1.590% 0.975%                                              0.565% 4.400%                           11.25 94.95% 25.26 1.617% 0.945% 0.528% 4.142%                               DPMSAA-0.45-1.5x2C 7.5 88.41% 35.33 1.500% 0.948% 0.454% 3.972%                                                        15 96.92% 20.14 1.615% 0.896%                                               0.381% 3.481%                           22.5 100.00% 13.61 1.807% 0.894% 0.416% 3.549%                               DPMSAA-0.45-1.5x2C (2ML) 3.75 62.82% 51.50 1.533% 1.030% 0.523% 4.535%                                                 7.5 87.35% 35.25 1.542% 0.942%                                              0.448% 4.101%                           11.25 94.30% 25.66 1.571% 0.915% 0.414% 3.793%                               DPMSAA-0.45/0.30-1.5x2C (2ML) 2.5 57.60% 66.41 1.480% 0.902% 0.709%                                                  4.875%                                  5 77.51% 44.63 1.530% 0.883% 0.683% 4.540%                                    7.5 87.41% 34.38 1.520% 0.846% 0.600% 4.208%                                 DPMSAA-0.45NW-1.5x2C 3.75 63.00% 54.30 1.501% 0.824% 0.693% 4.538%                                                    (2 ML) 7.5 84.20% 36.13 1.531%                                               0.808% 0.610% 4.034%                    11.25 93.44% 26.46 1.578% 0.802% 0.539% 3.707%                               DPMSAA-0.25-1.5x2C 3.75 67.68% 52.61 1.565% 0.952% 0.399% 4.190%                                                      (2 ML) 7.5 85.79% 33.77 1.552%                                               0.873% 0.405% 3.725%                    11.25 92.42% 24.34 1.623% 0.862% 0.412% 3.601%                               DPMSAA-0.10-1.5x2C 3.75 59.7% 50.28 1.666% 0.828% 0.267% 3.790%                                                       (2 mL) 7.5 77.5% 32.51 1.660%                                                0.801% 0.330% 3.580%                    11.25 85.64% 24.05 1.670% 0.777% 0.315% 3.440%                             __________________________________________________________________________     Note: "2 ML" means flow was 2 ml/min  otherwise flow is 1 ml/min              % is percent                                                                  conv. is conversion                                                           prod. is product Bisphenol A                                                  op/pp is the ratio of ortho, para bishpenol to para, parabisphenol tris i     higher                                                                        oligomeric adduct derived from the reaction of 2 acetone molecules with 3     phenol molecules                                                              cyclics are byproducts having dianins, spirobiindanols, and                   dihydroindanols.                                                              tot. imp. is total impurities including ortho, para bisphenol A, tris,        cyclics as well as other unidentified product peaks.                     

We claim:
 1. A catalytically-active material comprising an insolubleorganic or inorganic support in which is incorporated a polystyreneresin having a mercaptosulfonic acid residue represented by the formula##STR31## wherein n is an integer of from 0 to
 10. 2. Thecatalytically-active material of claim 1, wherein n is 2 or
 3. ##STR32##